Water-soluble unit dose articles comprising perfume

ABSTRACT

Described herein is a household care composition, which delivers active agents onto fabric, in the form of a water-soluble unit dose article comprising a water-soluble fibrous structure and a perfume, as well as methods for making the article and methods for treating fabrics using the article.

FIELD OF THE INVENTION

Described herein is a household care composition, which delivers activeagents onto fabric, in the form of a water-soluble unit dose articlecomprising a water-soluble fibrous structure and a perfume, as well asmethods for making the article and methods for treating fabrics usingthe article.

BACKGROUND OF THE INVENTION

Water-soluble unit dose articles are desired by consumers as theyprovide a convenient, efficient, and clean way of dosing a fabric orhard surface treatment composition. Water-soluble unit dose articlesprovide a measured dosage of a treatment composition, thereby avoidingover or under dosing. Fibrous water-soluble unit dose articles are ofincreasing interest to consumers. The technology related to sucharticles continues to advance in terms of providing the desired activeagents with the articles enabling the consumers to do the job that theywish to accomplish.

Consumers desire fibrous water-soluble unit dose articles that performas well or better than conventional forms of fabric treatmentcompositions, such as liquids, powders, and unit dose articlesconstructed of water-soluble films. Consumers also desire fibrouswater-soluble unit dose articles that deliver a fresh or clean scent towashed clothing, and fresh scent is a signal of efficacy. In particular,a consumer may smell a fibrous water-soluble unit dose article (at homeor in the store), enjoy the scent, and form an expectation that fabricstreated with the product will have a similarly intense scent, both afterthe laundry washing process and after the drying process. However, afterusing the fibrous water-soluble unit dose article, when the consumerremoves his or her clothing from the wash, he or she may notice that thescent of the clothing is not as intense as the scent of the fibrouswater-soluble unit dose article itself. After then drying the clothing,the consumer may notice that the scent of the clothing is even lessintense. Thus, the expectations of the consumer are not met. Sometimes,even when multiple products are used by the consumer, for example, afibrous water-soluble unit dose detergent plus a fabric softener (havingthe same scent) plus an in-wash scent additive (having the same scent),the consumer's expectations of scent are not met.

It is believed that a portion of the perfume in any fabric care product,whether the product is a laundry detergent, a fabric softener, or anin-wash scent additive, may not deposit on the fabric and instead may bedrained with the remaining wash liquor, at the end of the wash.Thereafter, the perfume that did deposit onto the fabric may be lost asthe clothing undergoes drying, especially if the drying processincorporates heat. One way formulators have tried to solve the problemof poor scent deposition and retention is by adding more perfume tofabric care products. However, perfumes are often neat oils and may beunstable when placed with other liquid ingredients, e.g., in a liquiddetergent. In addition, there may a limit as to how much perfume can beadded to a water-soluble, solid substrate, e.g., fibrous ply in afibrous water-soluble unit dose article, without causing leakage orpremature dissolution of the substrate.

In view of the above, there is a continuing unaddressed need for afibrous water-soluble unit dose article, that meets a consumer'sexpectation that fabrics treated with the product will have a scentsimilar in intensity to the scent of the product itself, both after thelaundry washing process and after the drying process.

SUMMARY OF THE INVENTION

The present disclosure relates to a water-soluble unit dose articlecomprising a water-soluble fibrous first ply superposed to awater-soluble fibrous second ply, where a concentrated perfumecomposition is positioned between the superposed plies, the concentratedperfume composition comprising from about 55% to about 90% by weight ofthe composition of a perfume and from about 10% to about 45% by weightof the composition of an oil-binding agent.

The present disclosure also relates to a water-soluble unit dose articlecomprising a water-soluble fibrous first ply superposed to awater-soluble fibrous second ply, wherein a concentrated perfumecomposition is positioned between the superposed plies, the concentratedperfume composition comprising a perfume and an oil-binding agent,wherein the concentrated perfume composition has a viscosity of fromabout 4 Pa-s to about 200 Pa-s when measured at 1 s⁻¹ at 20° C. asdetermined according to the Shear Viscosity Test Method described hereinand wherein the concentrated perfume composition has an onset of melt offrom about 5° C. to about 25° C. as determined according to theDifferential calorimetry Test Method described herein.

The present disclosure also relates a process for manufacturing awater-soluble unit dose article comprising the steps of: providing awater soluble fibrous first ply; providing a water soluble fibroussecond ply, preferably formed on a surface other than said first ply,wherein said second ply is separate from said first ply; providing aconcentrated perfume composition as described herein; placing saidconcentrated perfume composition on one or both of said first ply andsaid second ply; superposing said first ply and said second ply so thatsaid concentrated perfume composition is between said first ply and saidsecond ply; and joining a first portion of said first ply to a secondportion of said second ply to form said water soluble unit dose article.

The present disclosure also relates to a method of laundering using anarticle according to the present invention, comprising the steps of,placing at least one article according to the present invention into thewashing machine along with the laundry to be washed, and carrying out awashing or cleaning operation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a product.

FIG. 2 is a first ply having a first layer and a second layer.

FIG. 3 a manufacturing line for making plies of material.

FIG. 4 is a second ply being joined to a first ply to form a product.

FIG. 5 is a manufacturing line for making a two-ply product.

FIG. 6 is a cross section view of a two-ply product.

FIG. 7 is a cross section view of a two-ply product, each ply being amultilayer ply.

FIG. 8 is manufacturing line for making a three-ply product.

FIG. 9 is a cross section view of a three-ply product, each ply being amultilayer ply.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Features and benefits of the present invention will become apparent fromthe following description, which includes examples intended to give abroad representation of the invention. Various modifications will beapparent to those skilled in the art from this description and frompractice of the invention. The scope is not intended to be limited tothe particular forms disclosed and the invention covers allmodifications, equivalents, and alternatives falling within the spiritand scope of the invention as defined by the claims.

As used herein, the terms “product” and “article” are usedinterchangeably.

As used herein, the articles including “the,” “a” and “an” when used ina claim or in the specification, are understood to mean one or more ofwhat is claimed or described.

As used herein, “active agent” or “household care active agent” or“fabric care active agent” refers to any ingredient that may provide abenefit, either directly or indirectly, to the one or more fabrics.Non-limiting examples of benefits and/or improvements to a fabricinclude cleaning (for example by surfactants), stain removal, stainreduction, wrinkle removal, color restoration, static control, wrinkleresistance, permanent press, wear reduction, wear resistance, pillremoval, pill resistance, soil removal, soil resistance (including soilrelease), shape retention, shrinkage reduction, softness, fragrance,anti-bacterial, anti-viral, odor resistance, and odor removal.

As used herein, the term “discrete” refers to particles that arestructurally distinctive from each other either under naked human eyesor under electronic imaging devices, such as scanning electronmicroscope (SEM) and transmission electron microscope (TEM). Preferably,the discrete particles of the present invention are structurallydistinctive from each other under naked human eyes.

The terms “fibrous element” and “filaments” are used interchangeablyhere to refer to elongated particles having a length greatly exceedingits average cross-sectional diameter, i.e., a length-to-diameter aspectratio of at least 10:1, and preferably such elongated particles have anaverage cross-sectional diameter of no more than 1 mm.

As used herein, “Hydrophilic Index” or “HI” of a surfactant iscalculated by the following equation:

${HI} = {\frac{M_{h}}{M_{T}} \times 20}$

wherein M_(h) is the molecular weight of all hydrophilic groups in thesurfactant, wherein M_(T) is the total molecular weight of thesurfactant. Both M_(h) and M_(T) refer to weight average molecularweights. For example, linear alkylbenzene sulfonate with an averagealkyl chain length of about 11.8 has a HI value of about 4.97. Foranother example, C₁₂-C₁₄ alkyl sulfate has a HI value of about 6.98. Foryet another example, C₁₂-C₁₄ alkyl ethoxylated sulfate with an averageethoxylation degree of about 1 has a HI value of about 8.78, and C₁₂-C₁₄alkyl ethoxylated sulfate with an average ethoxylation degree of about 3has a HI value of about 11.57. For still another example, C₁₄-C₁₅ alkylethoxylated alcohol with an average ethoxylation degree of about 7 has aHI value of about 12.73, and C₁₂-C₁₄ alkyl ethoxylated alcohol with anaverage ethoxylation degree of about 9 has a HI value of about 14.72.

As used herein, the terms “include,” “includes” and “including” aremeant to be non-limiting.

As used herein, the term “particle” refers to a solid matter of minutequantity, such as a powder, granule, encapsulate, microcapsule, and/orprill. The particles of the present invention can be spheres, rods,plates, tubes, squares, rectangles, discs, stars or flakes of regular orirregular shapes, but they are non-fibrous.

The term “substantially free of or” “substantially free from” as usedherein refers to either the complete absence of an ingredient or aminimal amount thereof merely as impurity or unintended byproduct ofanother ingredient. A composition that is “substantially free” of/from acomponent means that the composition comprises less than about 0.5%,0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition,of the component.

As used herein, the term “unitary” refers to a structure containing aplurality of distinctive parts that are combined together to form avisually coherent and structurally integral article.

As used herein, the term “water-soluble” refers to the ability of asample material to completely dissolve in or disperse into water leavingno visible solids or forming no visibly separate phase, when at leastabout 25 grams, preferably at least about 50 grams, more preferably atleast about 100 grams, most preferably at least about 150 grams, of suchmaterial is placed in one liter (1 L) of deionized water at 20° C. andunder the atmospheric pressure with sufficient stirring. In other words,the unit dose article or fibrous element is capable of forming ahomogeneous solution with water at ambient conditions. “Ambientconditions” as used herein means 23° C.±1.0° C. and a relative humidityof 50%±2%. The water-soluble unit dose article 1 is a unitary productthat a consumer would retrieve from the unit dose article's 1 packagingand place within a washing machine.

As used herein the phrases “fabric care composition” and “fabric careproduct” includes compositions and formulations designed for treatingfabric. Such compositions include but are not limited to, laundrycleaning compositions and detergents, fabric softening compositions,fabric enhancing compositions, fabric freshening compositions, laundryprewash, laundry pretreat, laundry additives, spray products, drycleaning agent or composition, laundry rinse additive, wash additive,post-rinse fabric treatment, ironing aid, unit dose formulation, delayeddelivery formulation, detergent contained on or in a porous substrate ornonwoven sheet, and other suitable forms that may be apparent to oneskilled in the art in view of the teachings herein. Such compositionsmay be used as a pre-laundering treatment, a post-laundering treatment,or may be added during the rinse or wash cycle of the launderingoperation.

It should be understood that the term “comprise” includes alsoembodiments where the term “comprises” means “consists of” or “consistsessentially of.”

In this description, all concentrations and ratios are on a weight basisof the composition unless otherwise specified. All temperatures hereinare in degrees Celsius (° C.) unless otherwise indicated. All conditionsherein are at 20° C. and under the atmospheric pressure, unlessotherwise specifically stated. All molecular weights are determined byweight average number molecular weight unless otherwise specificallynoted.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

A water-soluble unit dose article 5 is shown in FIG. 1. Thewater-soluble unit dose article 5 can comprise a water soluble fibrousfirst ply 10 and water soluble fibrous second ply 15 that are superposedrelative to one another. The first ply 10 and second ply 15 are joinedto one another to form a unitary water-soluble unit dose article 5. Thewater-soluble unit dose article 5 can have a mass from about 50 mg toabout 30 g, optionally about 100 mg to about 20 g, optionally about 1 gto about 20 g. The water-soluble unit dose article 5 can have a lengthand width from about 5 mm to about 20 cm, optionally from about 1 cm toabout 10 cm, and a thickness from about 1 mm to about 2 cm, optionallyabout 2 mm to about 10 mm.

For the types of water soluble fibrous plies described herein, it can bechallenging to manufacture an individual ply that is rigid enough so asnot to be floppy when the consumer uses the product. The water-solubleunit dose article may have planar area of between about 1 cm² and about100 cm². The stiffness of a fibrous ply can be function of thickness ofthe ply, the strength and stiffness of the individual fibersconstituting the ply, the quantity of inter-fiber bonds, the degree andnature of entanglement of the fibers, and the strength of theinter-fiber bonds. For the fibers constituting the fibrous pliesdiscussed herein, it can be difficult to provide for sufficiently thickply, having sufficiently strong and stiff water soluble fibers, that aresufficiently inter-bonded and entangled with one another in a desiredstructure, and bonded with one another such that a ply made of suchfibers is not floppy under its self-weight.

Providing a multi-ply water-soluble unit dose article 5 can help toovercome these limitations. The increased thickness of the water-solubleunit dose article achieved by layering and joining plies can provide forhigher in-plane bending stiffness since the moment of inertia about thebending axis is increased. Such articles 5 are not as floppy as thinnersingle ply articles. Further, the increased thickness of such articles 5make them easier for the consumer to grasp and handle. Further multi-plyarticles 5 provide for positions interior to the article where activeagents, such as perfume, can be placed so that the consumer does notcome into contact with the active agent.

The plies of the water-soluble unit dose article 5 can be viewedhierarchically starting from the form in which the consumer interactswith the water soluble article 5 and working backward to the rawmaterials from which the plies are made.

I. Fibrous Plies A. Fibrous Structures

The fibrous plies can be fibrous structures. Fibrous structures compriseone or more fibrous elements. The fibrous elements can be associatedwith one another to form a structure.

Fibrous structures can include particles within and or on the structure.Fibrous structures can be homogeneous, layered, unitary, zoned, or asotherwise desired, with different active agents defining the variousaforesaid portions.

A fibrous structure can comprise one or more layers, the layers togetherforming the ply. For instance, as shown in FIG. 2, the first ply 10 cancomprise a first layer 20 and a second layer 25. The first layer 20 andsecond layer 25 can comprise a plurality of fibrous elements 30. Thefirst ply 10 can comprise a plurality of particles at a locationselected from the group consisting of the first layer 20, the secondlayer 25, between the first layer 20 and second layer 25, andcombinations thereof. A ply having a plurality of layers can be formedby depositing a plurality of fibrous elements 30 having a distinguishingcharacteristic to form a first layer 20 and then depositing a secondlayer 25 of fibrous elements 30 on top of the first layer 20. Forclarity, for multilayer plies, there can be intermingling of fibersconstituting the layers. Further, for clarity, there can beintermingling of fibers constituting the plies.

A fibrous structure can comprise a plurality of identical orsubstantially identical from a compositional perspective of fibrouselements 30. Optionally, the fibrous structure may comprise two or moredifferent fibrous elements 30. Non-limiting examples of differences inthe fibrous elements 30 may be physical differences such as differencesin diameter, length, texture, shape, rigidness, elasticity, and thelike; chemical differences such as crosslinking level, solubility,melting point, glass transition temperature, active agent,filament-forming material, color, level of active agent, basis weight,level of filament-forming material, presence of any coating on fibrouselement, biodegradable or not, hydrophobic or not, contact angle, andthe like; differences in whether the fibrous element 30 loses itsphysical structure when the fibrous element is exposed to conditions ofintended use; differences in whether the fibrous element's 30 morphologychanges when the fibrous element 30 is exposed to conditions of intendeduse; and differences in rate at which the fibrous element 30 releasesone or more of its active agents when the fibrous element 30 is exposedto conditions of intended use. In one example, two or more fibrouselements 30 and/or particles within the fibrous structure may comprisedifferent active agents.

The fibrous structure may exhibit different regions, such as differentregions of basis weight, density and/or caliper, surface texture,pattern of fibrous structure, embossing pattern, apertures, apertures ina pattern, and the like.

Non-limiting examples of use of the fibrous structure of die presentinvention include, but are not limited to household care compositions,including fabric care compositions.

The fibrous structure of the present invention may be used as is or maybe coated with one or more active agents.

B. Fibrous Elements

The fibrous elements 30 may be water soluble. The fibrous elements 30can comprise constituent material selected from the group consisting ofone or more filament forming materials, one or more active agents, andcombinations thereof. The active agents may be releasable from thefibrous elements 30, such as when the fibrous element 30 and/or fibrousstructure comprising the fibrous element 30 is exposed to conditions ofintended use.

The fibrous elements can comprise from about 5% to about 100% by weighton a dry fibrous element basis and/or dry fibrous structure basis of oneor more filament-forming materials. The fibrous elements can comprisefrom about 5% to about 100% by weight on a dry fibrous element basisand/or dry fibrous structure basis of one or more filament-formingmaterials and from about 5% to about 95% by weight by weight on a dryfibrous element basis and/or dry fibrous structure basis one or moreactive agents.

The fibrous elements can comprise more than about 50% by weight on a dryfibrous element basis and/or dry fibrous structure basis of one or morefilament-forming materials and less than about 50% by weight on a dryfibrous element basis and/or dry fibrous structure basis of one or moreactive agents.

The fibrous elements can comprise less than about 50% by weight on a dryfibrous element basis and/or dry fibrous structure basis of one or morefilament-forming materials and more than about 50% by weight on a dryfibrous element basis and/or dry fibrous structure basis of one or moreactive agents.

A fibrous element 30 can comprise one or more filament-forming materialsand one or more active agents selected from the group consisting of:enzymes, bleaching agents, builder, chelants, sensates, dispersants,perfumes, antimicrobials, antibacterials, antifungals, and mixturesthereof that are releasable and/or released when the fibrous elementand/or fibrous structure comprising the fibrous element is exposed toconditions of intended use.

The fibrous elements 30 may be meltblown fibrous elements 30, spunbondfibrous elements 30, hollow fibrous elements 30, or the like. Thefibrous elements 30 may be hydrophilic or hydrophobic. The fibrouselements 30 may be surface treated and/or internally treated to changethe inherent hydrophilic or hydrophobic properties of the fibrouselement. The fibrous elements 30 can have a diameter of less than about100 μm and/or less than about 75 μm and/or less than about 50 μm and/orless than about 25 μm and/or less than about 10 μm and/or less thanabout 5 μm and/or less than about 1 μm as measured according to theDiameter Test Method described herein. The fibrous elements 30 can havea diameter from about 1 μm to about 500 μm, optionally about 1 μm toabout 100 μm, optionally about 1 μm to about 50 μm, optionally about 1μm to about 30 μm, optionally about 5 μm to about 15 μm, optionallyabout 7 μm to about 15 μm according to the Diameter Test. Methoddescribed herein. The fibrous elements 30 can have a diameter of greaterthan about 1 μm as measured according to the Diameter Test Methoddescribed herein. The smaller the diameter the faster the rate ofrelease of the active agents and the rate of loss and or altering of thefibrous element's 30 physical structure.

The fibrous element 30 may comprise an active agent within the fibrouselement and an active agent on an external surface of the fibrouselement 30, such as an active agent coating on the fibrous element 30.The active agent on the external surface of the fibrous element 30 maybe the same or different from the active agent present in the fibrouselement 30. If different, the active agents may be compatible orincompatible with one another.

The one or more active agents may be uniformly distributed orsubstantially uniformly distributed throughout the fibrous element 30.The active agents may be distributed as discrete regions within thefibrous element 30. The at least one active agent can be distributeduniformly or substantially uniformly throughout the fibrous element 30and at least one other active agent is distributed as one or morediscrete regions within the fibrous element 30. Optionally, at least oneactive agent is distributed as one or more discrete regions within thefibrous element 30 and at least one other active agent is distributed asone or more discrete regions different from the first discrete regionswithin the fibrous element 30.

C. Filament Forming Material

The filament-forming material is any suitable material, such as apolymer or monomers capable of producing a polymer that exhibitsproperties suitable for making a filament, such as by a spinningprocess. The filament-forming material may comprise a polarsolvent-soluble material, such as an alcohol-soluble material and/or awater-soluble material, which can be beneficial for product applicationsthat include use of water.

The filament-forming material may comprise a non-polar solvent-solublematerial.

The filament-forming material may comprise a water-soluble material andbe free (less than 5% and/or less than 3% and/or less than 1% and/or 0%by weight on a dry fibrous element basis and/or dry fibrous structurebasis) of water-insoluble materials.

The filament-forming material may comprise a polymer selected from thegroup consisting of: polymers derived from acrylic monomers such as theethylenically unsaturated carboxylic monomers and ethylenicallyunsaturated monomers, polyvinyl alcohol, polyvinylformamide,polyvinylamine, polyacrylates, polymethacrylates, copolymers of acrylicacid and methyl acrylate, polyvinylpyrrolidones, polyalkylene oxides,starch and starch derivatives, pullulan, gelatin, and cellulosederivatives (for example, hydroxypropylmethyl celluloses, methylcelluloses, carboxymethy celluloses).

The filament-forming material may comprise a polymer selected from thegroup consisting of: polyvinyl alcohol, polyvinyl alcohol derivatives,starch, starch derivatives, cellulose derivatives, hemicellulose,hemicellulose derivatives, proteins, sodium alginate, hydroxypropylmethylcellulose, chitosan, chitosan derivatives, polyethylene glycol,tetramethylene ether glycol, polyvinyl pyrrolidone, hydroxymethylcellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and mixturesthereof.

The filament-forming material may comprise a polymer selected from thegroup consisting of: pullulan, hydroxypropylmethyl cellulose,hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl pyrrolidone,carboxymethylcellulose, sodium alginate, xanthan gum, tragacanth gum,guar gum, acacia gum, Arabic gum, polyacrylic acid, methylmethacrylatecopolymer, carboxyvinyl polymer, dextrin, pectin, chitin, levan,elsinan, collagen, gelatin, zein, gluten, soy protein, casein, polyvinylalcohol, carboxylated polyvinyl alcohol, sulfonated polyvinyl alcohol,starch, starch derivatives, hemicellulose, hemicellulose derivatives,proteins, chitosan, chitosan derivatives, polyethylene glycol,tetramethylene ether glycol, hydroxymethyl cellulose, and mixturesthereof.

1. Water-Soluble Materials

Non-limiting examples of water-soluble materials include water-solublepolymers. The water-soluble polymers may be synthetic or naturaloriginal and may be chemically and/or physically modified.

Non-limiting examples of water-soluble polymers include water-solublehydroxyl polymers, water-soluble thermoplastic polymers, water-solublebiodegradable polymers, water-soluble non-biodegradable polymers andmixtures thereof. The water-soluble polymer may comprise polyvinylalcohol. In another example, the water-soluble polymer may comprisestarch. The water-soluble polymer may comprise polyvinyl alcohol andstarch. The water-soluble polymer may comprise carboxymethyl cellulose.The polymer may comprise carboxymethyl cellulose and polyvinyl alcohol.

a. Water-Soluble Hydroxyl Polymers

Non-limiting examples of water-soluble hydroxyl polymers in accordancewith the present invention can be selected from the group consisting ofpolyols, such as polyvinyl alcohol, polyvinyl alcohol derivatives,polyvinyl alcohol copolymers, starch, starch derivatives, starchcopolymers, chitosan, chitosan derivatives, chitosan copolymers,cellulose derivatives such as cellulose ether and ester derivatives,cellulose copolymers, hemicellulose, hemicellulose derivatives,hemicellulose copolymers, gums, arabinans, galactans, proteins,carboxymethylcellulose, and various other polysaccharides and mixturesthereof.

Polyvinyl alcohols herein can be grafted with other monomers to modifyits properties. A wide range of monomers has been successfully graftedto polyvinyl alcohol. Non-limiting examples of such monomers includevinyl acetate, styrene, acrylamide, acrylic acid, 2-hydroxyethylmethacrylate, acrylonitrile, 1,3-butadiene, methyl methacrylate,methacrylic acid, maleic acid, itaconic acid, sodium vinylsulfonate,sodium allylsulfonate, sodium methylallyl sulfonate, sodiumphenylallylether sulfonate, sodium phenylmethallylether sulfonate,2-acrylamido-methyl propane sulfonic acid (AMPs), vinylidene chloride,vinyl chloride, vinyl amine and a variety of acrylate esters.

In one example, the water-soluble hydroxyl polymer is selected from thegroup consisting of: polyvinyl alcohols, hydroxymethylcelluloses,hydroxyethylcelluloses, hydroxypropylmethylcelluloses,carboxymethylcelluloses, and mixtures thereof. A non-limiting example ofa suitable polyvinyl alcohol includes those commercially available fromSekisui Specialty Chemicals America, LLC (Dallas, Tex.) under the CELVOL(Registered trademark) trade name. Another non-limiting example of asuitable polyvinyl alcohol includes G Polymer commercially availablefrom Nippon Ghosei. A non-limiting example of a suitablehydroxypropylmethylcellulose includes those commercially available fromthe Dow Chemical Company (Midland, Mich.) under the METHOCEL (Registeredtrademark) trade name including combinations with above mentionedpolyvinyl alcohols.

b. Water-Soluble Thermoplastic Polymers

Non-limiting examples of suitable water-soluble thermoplastic polymersinclude thermoplastic starch and/or starch derivatives, polylactic acid,polyhydroxyalkanoate, polycaprolactone, polyesteramides and certainpolyesters, and mixtures thereof. The water-soluble thermoplasticpolymers may be hydrophilic or hydrophobic. The water-solublethermoplastic polymers may be surface treated and/or internally treatedto change the inherent hydrophilic or hydrophobic properties of thethermoplastic polymer. The water-soluble thermoplastic polymers maycomprise biodegradable polymers. Any suitable weight average molecularweight for the thermoplastic polymers may be used. For example, theweight average molecular weight for a thermoplastic polymer inaccordance with the present invention can be greater than about 10,000g/mol and/or greater than about 40,000 g/mol and/or greater than about50,000 g/mol and/or less than about 500,000 g/mol and/or less than about400,000 g/mol and/or less than about 200,000 g/mol.

D. Filament-Forming Composition

The fibrous elements 30 of the present invention are made from afilament-forming composition. The filament-forming composition can be apolar-solvent-based composition. In one example, the filament-formingcomposition is an aqueous composition comprising one or morefilament-forming materials and one or more active agents.

The filament-forming composition of the present invention may have ashear viscosity as measured according to the Shear Viscosity Test Methoddescribed herein of from about 1 Pascal·Seconds to about 25Pascal·Seconds and/or from about 2 Pascal·Seconds to about 20Pascal·Seconds and/or from about 3 Pascal·Seconds to about 10Pascal·Seconds, as measured at a shear rate of 3,000 sec−1 and at theprocessing temperature (50 deg. C. to 100 deg. C.). The filament-formingcomposition may be processed at a temperature of from about 25 deg. C.to about 100 deg. C. and/or from about 65 deg. C. to about 95 deg. C.and/or from about 70 deg. C. to about 90 deg. C. when making fibrouselements 30 from the filament-forming composition.

In one example, the filament-forming composition may comprise at least20% and/or at least 30% and/or at least 40% and/or at least 45% and/orat least 50% to about 90% and/or to about 85% and/or to about 80% and/orto about 75% by weight of one or more filament-forming materials, one ormore active agents, and mixtures thereof. The filament-formingcomposition may comprise from about 10% to about 80% by weight of apolar solvent, such as water.

In a fibrous element spinning process, the fibrous elements 30 need tohave initial stability as they leave the spinning die. Capillary numberis used to characterize this initial stability, criterion. At theconditions of the die, the capillary number can be from about 0.5 toabout 10, at least 1 and/or at least 3 and/or at least 4 and/or at least5.

In one example, the filament-forming composition exhibits a capillarynumber of from about 1 to about 50 and/or about 3 to about 50 and/orabout 5 to about 30 such that the filament-forming composition can beeffectively polymer processed into a fibrous element.

“Polymer processing” as used herein means any spinning operation and/orspinning process by which a fibrous element comprising a processedfilament-forming material is formed from a filament-forming composition.The spinning operation and/or process may include spunbonding, meltblowing, electro-spinning, rotary spinning, continuous filamentproducing and/or tow fiber producing operations/processes. A “processedfilament-forming material” as used herein means any filament-formingmaterial that has undergone a melt processing operation and a subsequentpolymer processing operation resulting in a fibrous element.

The capillary number is a dimensionless number used to characterize thelikelihood of this droplet breakup. A larger capillary number indicatesgreater fluid stability upon exiting the die. The capillary number,c_(a), is defined as follows:

$c_{a} = \frac{V\; \eta}{\sigma}$

Where V is the average fluid velocity at the die exit (units of Lengthper Time), η is the fluid viscosity at the conditions of the exit of thedie (units of Mass per Length*Time), σ is the surface tension of thefluid (units of Mass per Time²).

In one example, the filament-forming composition may comprise one ormore release agents and/or lubricants. Non-limiting examples of suitablerelease agents and/or lubricants include fatty acids, fatty acid salts,fatty alcohols, fatty esters, sulfonated fatty acid esters, fatty amineacetates and fatty amides, silicones, aminosilicones, fluoropolymers andmixtures thereof.

In one example, the filament-forming composition may comprise one ormore antiblocking and/or detackifying agents. Non-limiting examples ofsuitable antiblocking and/or detackifying agents include starches,modified starches, crosslinked polyvinylpyrrolidone, crosslinkedcellulose, microcrystalline cellulose, silica, metallic oxides, calciumcarbonate, talc and mica.

Active agents of the present invention may be added to thefilament-forming composition prior to and/or during fibrous elementformation and/or may be added to the fibrous element after fibrouselement formation. For example, a perfume active agent may be applied tothe fibrous element and/or fibrous structure comprising the fibrouselement after the fibrous element and/or fibrous structure according tothe present invention are formed. In another example, an enzyme activeagent may be applied to the fibrous element and/or fibrous structurecomprising the fibrous element after the fibrous element and/or fibrousstructure according to the present invention are formed. In stillanother example, one or more particles, which may not be suitable forpassing through the spinning process for making the fibrous element, maybe applied to the fibrous element and/or fibrous structure comprisingthe fibrous element after the fibrous element and/or fibrous structureaccording to the present invention are formed.

E. Extensional Aids

In one example, the fibrous element comprises an extensional aid.Non-limiting examples of extensional aids can include polymers, otherextensional aids, and combinations thereof. High molecular weightextensional aids can be used since they have the ability to increaseextensional melt viscosity and reduce melt fracture.

The extensional aid, when used in a meltblowing process, is added to thecomposition of the present invention in an amount effective to visiblyreduce the melt fracture and capillary breakage of fibers during thespinning process such that substantially continuous fibers havingrelatively consistent diameter can be melt spun. The extensional aidscan be present from about 0.001% to about 10%, by weight on a dryfibrous element basis and/or dry particle basis and/or dry fibrousstructure basis, in one example, and in another example from about 0.005to about 5%, by weight on a dry fibrous element basis and/or dryparticle basis and/or dry fibrous structure basis, in yet anotherexample from about 0.01 to about 1%, by weight on a dry fibrous elementbasis and/or dry particle basis and/or dry fibrous structure basis, andin another example from about 0.05% to about 0.5%, by weight on a dryfibrous element basis and/or dry particle basis and/or dry fibrousstructure basis.

Non-limiting examples of polymers that can be used as extensional aidscan include alginates, carrageenans, pectin, chitin, guar gum, xanthumgum, agar, gum arabic, karaya gum, tragacanth gum, locust bean gum,alkylcellulose, hydroxyalkylcellulose, carboxyalkylcellulose, andmixtures thereof. Nonlimiting examples of other extensional aids caninclude modified and unmodified polyacrylamide, polyacrylic acid,polymethacrylic acid, polyvinyl alcohol, polyvinylacetate,polyvinylpyrrolidone, polyethylene vinyl acetate, polyethyleneimine,polyamides, polyalkylene oxides including polyethylene oxide,polypropylene oxide, polyethylenepropylene oxide, and mixtures thereof.

F. Method for Making Fibrous Elements and Plies

The fibrous elements 30 and plies formed therefrom may be made by anysuitable process. A non-limiting example of a suitable process formaking the plies and continuous ply webs is shown in FIG. 3. A solutionof a filament forming composition 35 is provided. The filament formingcomposition can comprise one or more filament forming materials andoptionally one or more active agents. The filament forming composition35 is passed through one or more die block assemblies 40 comprising aplurality of spinnerets 45 to form a plurality of fibrous elements 30comprising the one or more filament forming materials and optionally oneor more active agents. Multiple die block assemblies 40 can be employedto spin different layers of fibrous elements 30, with the fibrouselements 30 of different layers having a composition that differ fromone another or are the same as one another. That is, the filamentforming composition 35 provided to one die block assembly 40 can differcompositionally from the filament forming composition 35 provided toanother die block assembly 40. More than two die block assemblies inseries can be provided to form three, four, or any other integer numberof layers in a given ply.

The fibrous elements 30 can be deposited on a belt 50 moving in amachine direction MD to form a first ply 10. The belt 50 can be aforaminous belt.

Belts 50 that are air permeable are desirable so that vacuum can beapplied to and through the belt. The belt 50 can be a XBE2A9 beltavailable from F.N. Sheppard & Co. Erlanger, Ky., USA. The belt 50 canbe formed from polyester strands or other polymeric strands. It isdesirable that the belt 50 have small openings so that the web carriedthereon is not deformed into the openings. The belt 50 can be coated tolower the surface tension of the belt 50 with respect to the web carriedthereon. The belt 50 can move at a speed from about 1 m/min to about 100m/min, optionally about 2 m/min to about 30 m/min.

The motive force to move the continuous ply webs disclosed herein may beprovide by one or more belts 50. As the belt 50 moves die continuous plywebs ride directly or indirectly through another material, for exampleanother continuous ply web, on the belt 50. For locations at which thecontinuous ply web are not in contact with a belt 50, tensile forcemobilized in the continuous ply web downstream of the location at whichthe continuous ply web loses contact with the belt 50 can pull thecontinuous ply web along. Optionally, when a continuous ply web is offof the belt, motive force can be provided by motorized rollers.

The spinnerets 45 may comprise a plurality of fibrous element-formingholes that include a melt capillary encircled by a concentricattenuation fluid hole through which a fluid, such as air at atemperature from about 10 C to about 100 C, can pass to facilitateattenuation of the filament-forming composition 35 into a fibrouselement 30 as it exits the fibrous element-forming hole. Thefilament-forming composition can be provided to the fibrous-elementforming hole at a rate of about 0.1 to about 2 g/min per hole, which canbe set based on the composition of the filament-forming composition.

During the spinning step, volatile solvent, such as water, present inthe filament-forming composition 35 can be removed, such as by drying,as the fibrous element 30 is formed. Greater than 30% and/or greaterthan 40% and/or greater than 50%, and/or greater than 60% of the weightof the filament-forming composition's volatile solvent, such as water,can be removed during the spinning step, such as by drying the fibrouselement being produced.

The filament-forming composition is spun into one or more fibrouselements 30 and/or particles by any suitable spinning process, such asmeltblowing, spunbonding, electro-spinning, and/or rotary spinning. Inone example, the filament-forming composition is spun into a pluralityof fibrous elements 30 and/or particles by meltblowing. For example, thefilament-forming composition may be pumped from a tank to a meltblownspinnerette. Upon exiting one or more of the filament-forming holes inthe spinnerette, the filament-forming composition is attenuated with airto create one or more fibrous elements 30 and/or particles. The fibrouselements 30 and/or particles may then be dried to remove any remainingsolvent used for spinning, such as the water.

The fibrous elements 30 and/or particles of the present invention may becollected on a belt, such as a patterned belt or flat belt, to form afibrous structure comprising the fibrous elements 30 and/or particlesthat are directed into the fibrous elements 30 30.

Particles can be introduced into the stream of the fibrous elements 30between the die block assembly 40 and the belt 50. Particles can be fedfrom a particle receiver onto a belt feeder 41 or optionally a screwfeeder. The belt feeder 41 can be set and controlled to deliver thedesired mass of particles into the process. The belt feeder can feed anair knife 42 that suspends and directs the particles in an air streaminto the fibrous elements 30 to form a mixture of comingled fibrouselements 30 and particles that are subsequently deposited on the belt50. Optionally, particles can be introduced after the fibrous elements30 are deposited on the belt 50. Optionally, the particles can beintroduced by gravity and or optionally in between streams offilament-forming composition. An air laid forming head or sifter can beused to introduce the particles.

Multi-layer plies can be formed by providing two die block assemblies40, one die block assembly 40 downstream of another die block assembly40, by way of nonlimiting example as shown in FIG. 3.

A pressurized tank suitable for batch operation can be filled with asuitable filament-forming composition 35 for spinning. A pump, such as aZENITH, type PEP II, having a capacity of 5.0 cubic centimeters perrevolution (cc/rev), manufactured by Parker Hannifin Corporation, ZenithPumps division, of Sanford, N.C., USA may be used to facilitatetransport of the filament-forming composition 35 to the spinnerets 45.

The die block assembly 40 can have several rows of circular extrusionnozzles (fibrous element-forming holes) spaced from one another at apitch P of about 1.524 millimeters. The nozzles can have individualinner diameters of about 0.305 millimeters and individual outsidediameters of about 0.813 millimeters. Each individual nozzle can beencircled by an annular and divergently flared orifice (concentricattenuation fluid hole to supply attenuation air to each individual meltcapillary). The filament-forming composition 35 extruded through thenozzles can be surrounded and attenuated by generally cylindrical,humidified air streams supplied through the orifices.

Attenuation air can be provided by heating compressed air from a sourceby an electrical-resistance heater, for example, a heater manufacturedby Chromalox, Division of Emerson Electric, of Pittsburgh, Pa., USA. Anappropriate quantity of steam can be added to saturate or nearly,saturate the heated air at the conditions in the electrically heated,thermostatically controlled delivery pipe. Condensate can be removed inan electrically heated, thermostatically controlled, separator.

The embryonic fibrous elements 30 can be dried by a drying air streamhaving a temperature from about 149 C to about 315 C by an electricalresistance heater supplied through drying nozzles and discharged at anangle of about 90 degrees or less relative to the general orientation ofthe non-thermoplastic embryonic fibers being extruded. The driedembryonic fibrous elements 30 can be collected on a collection device,such as a movable foraminous belt, patterned collection belt, or flatbelt. The addition of a vacuum source directly under the formation zonemay be used to aid collection of the fibers.

II. Process for Manufacturing a Water Soluble Product

The various water soluble fibrous plies disclosed herein can be used tomanufacture water soluble products 5. The process for manufacturing canbe performed on discrete plies of material. Discrete plies of materialare individual pieces of the various plies described herein that areassembled and joined in some manner to form a single water solubleproduct 5. Optionally, the process for manufacturing can be performed oncontinuous ply webs described herein that are assembled and joined insome manner and are cut to form multiple water soluble products 5.

The process of manufacturing a water soluble product 5 can comprise thefollowing steps as illustrated in FIG. 4. A water soluble first ply 10can be provided. A water soluble second ply 15 can be provided separatefrom the first ply 10. The first ply 10 and the second ply 15 aresuperposed with one another. By superposed it is meant that one ispositioned above or below the other with the proviso that additionalplies or other materials, for example active agents, such as perfume,may be positioned between the superposed plies. A portion of the firstply 10 can be joined to a portion of the second ply 15 to form the watersoluble product 5. Importantly, the second ply 15 can be formed on asurface 52 other than the first ply 10. That is second ply 15 isoptionally not formed on the first ply 10 as might occur if a pluralityof fibrous elements 30 are discharged from a first die block assembly 40onto a belt 50 to form a first ply 10 of material and then anotherplurality of fibrous elements 30 is discharged from a second die blockassembly 40 on top of the first ply 10 to form a second ply 15 on top ofthe first ply 10.

Each ply may comprise one or more layers. A ply formed of multiplelayers can have coherency amongst two or more of the layers to form anintegral ply. There can be intermingling of fibers constituting layersof a ply and intermingling of fibers between plies that are next to oneanother.

The second ply 15 can be cut from the first ply 10, in which case thesecond ply 15 and first ply 10 can be formed on the same forming surfaceand be integral with one another at the time and location of formation.It might be advantageous to not form one ply on top of another becausesuch a construction will have one surface that is a belt side having atexture that might differ from the air side of the of such construction.That can make it difficult to print on both sides of the product 5,result in one side being more prone to leak particles as compared toanother side if particles are provided in or on a layer, and result in aproduct 5 that has one side that differs in surface texture or hand thanthe other, which can be confusing to a consumer as he or she may thinkthat the different sides of the product 5 may have a different function.

By joined it is meant that the elements are attached or connecteddirectly to one another or are attached or connected to one anotherindirectly through one or more intermediate elements that are attachedor connected to the element being referred to as joined.

More practically, the first ply 10 can be provided as part of a firstcontinuous ply web 60 and the second ply 15 can be provided as part of asecond continuous ply web 65, by way of non-limiting example as shown inFIG. 5. FIG. 5 is a nonlimiting example of how a two-ply product 5 canbe formed. First continuous ply web 60 and the second continuous ply web65 can be superposed to superpose what ultimately becomes the first ply10 and the second ply 15 in a product 5. At this stage of the process,what ultimately becomes the individual water soluble products 5 can bepart of a continuous multi-ply webs. There can be intermingling offibers constituting the plies. This may occur when the plies forming theproduct 5 are brought into contact with one another and or bonded to oneanother.

It can be practical to spin a first continuous ply web 60 having a widthfrom about 20 cm to about 500 cm, or from about 20 cm to about 100 cm,or from about 20 cm to about 80 cm, or from about 40 cm to about 70 cm,or about 60 cm. Such a first continuous ply web 60 can be cut in themachine direction MD to form multiple plies that can be stacked form oneor more products 5 in on or more lanes of product 5 production. Forinstance, it can be practical to provide a first continuous ply web 60that is about 60 cm wide and cut it into three continuous plies eachhaving a width of about 20 cm, stack those three continuous plies, jointhose three plies together, to form two or more products 5 in the crossdirection CD.

In FIG. 5, product 5 making reduces down to a single lane with thepotential for making multiple products 5 in the cross direction.Optionally, there can be multiple product making lanes fed by a wide webformed from a wide die assembly 40. The wide web can be slit in themachine direction to form a plurality of first continuous ply webs 60and second continuous ply webs 65 so that multiple lanes of productmaking are possible. For example, a duplicate of the apparatus shown inFIG. 5 could be positioned immediately next to the apparatus shown inFIG. 5 but a single die assembly 40 could feed a wide continuous ply webinto the individual lanes of product making, with the cutting knife 70configured to separate out the continuous ply webs as appropriate tofeed the individual lanes of product 5 making.

After the step of superposing the first ply 10 and second ply 15, thesuperposed first continuous ply web 60 and second continuous ply web 65can be joined to one another and cut to form the water soluble product5. A first portion 11 of the first ply 10 can be joined to a secondportion 16 of the second ply 15 to the water soluble product 5.

The first continuous ply web 60 can be provided separately from thesecond continuous ply web 65. For instance, the first continuous ply web60 can be formed using a die block assembly 40 that is separate from thedie block assembly 40 used to make the second continuous ply web 65.Optionally the first continuous ply web 60 and second continuous ply web65 can be supplied as separate parent rolls of such materials. It can bepractical to employ a continuous process from formation of the plies tofinished product 5 because it can be challenging to handle and storewater soluble fibrous webs.

The second continuous ply web 65 can be cut from the first continuousply web 60. For instance, the first continuous ply web 60 can be formedon a die block assembly 40 and then cut in the machine direction MD by aknife 70, as shown in FIG. 5, for instance a rotary cutting knife thatcuts in the machine direction MD. Cutting ply webs from the firstcontinuous ply web 60 can be practical for providing bettermanufacturing quality control since only a single die block assemblymust be controlled and control ends up being universally applied to eachply web. This contrasts to the situation in which one die block is usedto form one ply and another die block is used to form another ply andboth die blocks must be carefully monitored and controlled. Also, suchan arrangement can be helpful for minimizing trimming waste that mightbe required for edges of the ply web which may be thinner than portionsof the ply web nearer to the centerline of the ply web in the machinedirection MD. Thin edges of the plies can result in the need to processand handle plies and products 5 that have a nonuniform caliper, forinstance by trimming edges having reduced caliper or paying carefulattention to the orientation in which plies are superposed to form aproduct 5.

The process can further comprise a step of positioning the first plybelt side 75 and the second ply belt side 80 to face away from oneanother prior to joining the first ply 10 and the second ply 15. Thiscan be accomplished by providing only a single 180 degree twist in thesecond continuous ply web 65. The first ply belt side 75 is the side ofthe first ply 10 that was formed in contact with a surface 52 or belt50. In FIG. 5, the second continuous ply web 65 is twisted 90 degreestwice so that the second ply air side 85 faces away from the first plybelt side 75. One or both of the first continuous ply web 60 and secondcontinuous ply web 65 can be twisted 0 degrees, which could be twistedand untwisted by the same number of degrees, 180 degrees (for exampleright hand or left hand twist of 180 degrees, optionally in two 90degree steps) or 360 degrees prior to bringing the first continuous plyweb 60 and second continuous ply web 65 into facing relationship toobtain the desired positioning of the first ply belt side 75, first plyair said 90, second ply belt side 80, and second ply air side 85,relative to one another. It can be practical for the first ply air side90 (or first continuous ply web air side) and second ply air side 85 (orsecond continuous ply web air side) to be in contact with one anotherand for the first ply belt side 75 (or first continuous ply web beltside) and second ply belt side 80 (or second continuous ply web beltside) to be facing away from one another with the first ply air side 90and the second ply air side 85 (or second continuous ply web air side)between the first ply belt side 75 (or first continuous ply web beltside) and the second ply belt side 80 (or second continuous ply web beltside). Such an arrangement can position the belt side of the plies orcontinuous ply webs to face outwardly and ultimately form the exteriorsurface of the product 5 which can provide for a better tactile feel andor a surface upon which printing is convenient. Further, if multilayerplies or continuous ply webs are employed and particles are provided inone of the layers of the multilayer plies the belt side can act as abarrier to contain the particles and separate the consumer's hand fromthe particles.

If a step of the process further comprises a step of positioning thefirst ply belt side 75 and the second ply belt side 80 to face away fromone another prior to joining the first ply 10 and the second ply 15,such step can occur by twisting one of the first continuous ply web 60or second continuous ply web 65 180 degrees and placing the firstcontinuous ply web 60 and second continuous ply web 65 in facingrelationship with one another. The twisting of a continuous ply web canbe performed by lifting the continuous ply web from the belt 50,twisting the continuous ply web 180 or 360 degrees, and placing thecontinuous ply web that was twisted to be in facing relationship withthe other continuous ply web.

Twisting can be facilitated by lifting the continuous ply web with oneor more, or a system of, turning bars 77. For instance, a turning bar 77can be placed proximal the belt 50 and the continuous ply web can be fedaround the turning bar 77 upwards. The continuous ply web can be twistedthe desired amount and fed onto an elevated turning bar 77. Thecontinuous ply web can be moved in the cross direction CD to bepositioned above the other continuous ply web and fed over anotherturning bar 77. Then the continuous ply web can be fed downward and overanother turning bar 77 proximal the belt 50 to be in facing relationshipwith the other continuous ply web. Other ways known in the art forflipping a continuous web can be employed, such as a contoured invertingsurface.

The turning bars 77 may be static polished metal turning bars 77 or maybe turning bars 77 that rotate about an axis driven by a motor or thedrag force of the continuous ply web passing the turning bars 77, suchas a roller. The turning bars 77 may be polished metal turning bars 77to permit the continuous ply web to slide over the turning bars 77 withinconsequential drag force from the turning bars 77 so that thecontinuous ply web is not stretched more than is tolerable.

The first continuous ply web 10 can be considered to have a first plybelt side 75 and a first ply air side 90 opposite the first ply beltside 75. Similarly, the second continuous ply web 65 can be consideredto have a second ply belt side 80 and a second ply air side 85 oppositethe second ply belt side 80.

The belt side and air side of the plies can have a difference in surfacetexture. The belt side of a ply or continuous ply web is the side of theply or continuous ply web that was formed in contact with the belt 50upon which the fibrous elements 30 were deposited. That is, the beltside of a ply or continuous ply web can be the side of ply or continuousply web facing and in contact with the belt 50 upon which fibrouselements 30 were deposited. The belt side can tend to have a flattersurface profile than the air side since the fibrous elements 30 mayconform or partially conform to the surface 52 of the belt 50 on whichthe fibrous elements 30 land. The air side has no constraining surface.Absent post deposition processing, the air side of the plies may tend tobe fluffier or loftier, possibly less coherent, than the belt side.Providing products 5 that have the belt sides of the plies facingoutwardly can be practical for presenting the smoother surfaces of theplies outwardly for subsequent printing, better tactile feel and look,and better ability to contain particles. Also, if multilayer plies areprovided, plies containing particles can confined to the interior of theproduct 5 so that the user does not have or has limited contact with theparticles, which may comprise active agents.

One or more of the plies may be provided with particles comprising oneor more active agents, by way of nonlimiting example as shown in FIG. 6.For instance, the first ply 10 can be provided with a first plurality 91of water soluble first particles 95. Similarly, the second ply 15 can beprovided with a second plurality 100 of water soluble second particles105. The first particles 95 can be compositionally the same as thesecond particles 105. This might be convenient if the second ply 15 iscut from the first ply 10, by way of nonlimiting example as shown inFIG. 5, without regard to the twisting and superposing steps downstreamof knife 70.

Optionally, the outer surfaces of the product 5 can comprise the beltside surfaces of the plies. For instance, the first ply belt side 75 andthe second ply belt side 80 can positioned to face away from one anotherprior to joining the first ply 10 and second ply 15. Describedotherwise, the first ply air side 90 and the second ply air side 85 canface towards one another prior to joining the first ply 10 and secondply 15. Possible benefits to such a construction are discussedpreviously.

The process of manufacturing described herein may be convenientlyemployed fabricate products 5 having multiple plies and optionallymultilayer plies. Multiple plies and multilayer plies enable themanufacturer to provide for different product benefits in each ply orlayer, active agents away from the layers forming the outer surface ofthe products 5, surfaces that are convenient to print upon, and products5 that are pleasant to touch.

The process of manufacturing described herein can further comprise thesteps of providing a fibrous first layer 20 and providing a fibroussecond layer 25 facing, or in facing relationship with, the fibrousfirst layer 20. There can be intermingling of fibers constituting thefirst layer 10 and fibers constituting the second layer 25. As shown inFIG. 7, the first ply 10 can comprise a fibrous first layer 20 and afibrous second layer 25. The first layer 20 and the second layer 25 cantogether form the first ply 10. The second layer 25 and the first layer20 can be in facing and contacting relationship with one another, forinstance as would occur if the second layer 25 is deposited on the firstlayer 20. The second layer 25 can comprise a first plurality 91 of watersoluble first particles 95 distributed within the second layer 25. Theprocess of manufacturing described herein can further comprise the stepsof providing a fibrous third layer 110 and providing a fibrous fourthlayer 115 facing, or in facing relationship with, the fibrous thirdlayer. The third layer 110 and the fourth layer 115 can be in facing andcontacting relationship with one another, for instance as would occur ifthe fourth layer 115 is deposited on the third layer 110.

The second ply 15 can comprise the fibrous third layer 110 and thefibrous fourth layer 115. The third layer 110 and the fourth layer 115can together form the second ply 15. The fourth layer 115 can comprise asecond plurality 100 of water soluble second particles 105 distributedwithin the fourth layer 115. Providing multilayer plies can tend toenhance the stiffness of the product 5. Further multilayer plies enablethe product designer to place active agents in chosen layers of theplies, optionally provide for different active agents in differentlayers of the plies, and optionally place active agents between thelayers and or plies.

Multilayer ply webs can be formed as illustrated in FIG. 3, by way ofnonlimiting example. Each ply web can be formed independently of othersby employing multiple die block assemblies 40. And optionally, firstparticles 95, second particles 105, and third particles can beintroduced as described herein.

Each of the third layer 110 and the first layer 20 can have a basisweight from about 20 gsm to about 500 gsm, optionally about 40 gsm toabout 100 gsm, optionally about 50 gsm to 80 gsm, according to the BasisWeight Test Method. Each of second layer 25 and the fourth layer 115 canhave a basis weight from about 20 gsm to about 500 gsm, optionally about40 gsm to about 300 gsm, optionally about 200 gsm, according to theBasis Weight Test Method.

Any embodiments contemplated herein, the first continuous ply web 60,second continuous ply web 65, and third continuous ply web 130 (ifpresent) can have a basis weight from about 100 gsm to about 800 gsm,optionally from about 150 gsm to about 500 gsm, optionally about 200 gsmto about 300 gsm, according to the Basis Weight Test Method.

To provide for products 5 having surfaces that are easy to print uponand are pleasant to touch, it can be practical to have the belt facingsurfaces of the plies forming the outer surface of the product 5. Asshown in FIG. 7, the first layer 20 can be oriented towards a first plybelt side 75 and the second layer 25 can be oriented towards a first plyair side 90. The first ply air side 90 can be opposite the first plybelt side 75. The third layer 110 can be oriented towards the second plybelt side 80 and the fourth layer 115 can be oriented towards a secondply air side 85. The second ply air side 85 can be opposite the secondply belt side 80. The process of manufacturing the product 5 cancomprise the further step of positioning the first ply belt side 75 andthe second ply belt side 80 to face away from one another prior tojoining the first ply 10 and the second ply 15. This arrangement canprovide a benefit of positioning the first particles 95 and secondparticles 105 towards the interior of the product 5 and remote frombeing in contact with the consumer's hand as the product is handled. Inthis arrangement, the second layer 25 and the fourth layer 115 can bebetween the first layer 20 and the third layer 110.

It can be practical to provide the first layer 20 to have fewer firstparticles 95 than the second layer 25 and a further the fifth layer ifpresent. The first layer 20 can be free of or substantially free offirst particles 95. Optionally the second layer 25 can be free of orsubstantially free of second particles 105. Similarly, the fifth layer,if present, can be free of or substantially free of third particles.Such an arrangement can be practical for minimizing consumer exposure tothe active agents in particles and or active agents that are in thefibrous elements 30 forming the second layer 25 and or fourth layer 115or any other layer that is interior to layers forming the surface of theproduct 5.

A three-ply product 5 can also be practical. A nonlimiting example ofthe process to make a three-ply product 5 is shown in FIG. 8. To make athree-ply product 5, the process further comprises the step of providinga water soluble fibrous third ply 120. The third ply 120 can be separatefrom the first ply 10 and second ply 15. The first ply 10, second ply15, and third ply 120 can be superposed with one another so that thethird ply 120 is between the first ply 10 and second ply 15. The firstply 10, second ply 15, and third ply 120 can be joined to form the watersoluble product 5.

The third ply 120 can be provided as part of a third continuous ply web130. Conveniently, the third continuous ply web 130 can be cut in themachine direction (MD) from the first continuous ply web 60. Forinstance, a first continuous ply web 60 can be provided by depositingfibrous elements 30 onto a belt 50. Optionally, particles can beintroduced into the stream of fibrous elements 30 between the die blockassembly 40 and the belt 50. Further optionally, particles can beintroduced onto the air side of the first continuous ply web 60. Thesecond continuous ply web 65 and the third continuous ply web 130 can becut from the first continuous ply web 60. A third continuous ply web 130is considered to be cut in the machine direction MD from the firstcontinuous ply web 60 if it is cut in the machine direction MD from thesecond continuous ply web 65 after the second continuous ply web 65 iscut in the machine direction MD from the first continuous ply web 60.

In one configuration of the process, three lanes 125 of separatecontinuous ply webs can be provided in the machine direction MD. Thelanes of continuous ply webs may be in any order in the cross directionand web handling appurtenances may be used to lift individual continuousply webs from the belt 50 and lay them onto another continuous ply webwith either the belt side or air side facing up. Starting with a singlecontinuous ply web such as the first continuous ply web 60 and cuttingfrom that ply web the second continuous ply web 65 and third continuousply web 130 can simplify manufacturing quality control since only asingle die block assembly 40 and optionally a particle providingapparatus need to be monitored and controlled. Optionally, each of thecontinuous ply webs can be formed by one or more separate die blockassemblies 40.

After superposing the first continuous ply web 60, second continuous plyweb 65, and third continuous ply web 130, such continuous ply webs canbe cut to form the water soluble product 5. Optionally, two or more ofsuch continuous ply webs can first be joined to one another and then cutto form the water soluble product 5. Optionally, the step of joining twoor more of the continuous ply webs and cutting such webs to form thewater soluble product 5 can be combined in a single step. Furtheroptionally, such continuous ply webs can be cut to provide the first ply10, second ply 15, and third ply 120, before joining two or more of suchplies to form the water soluble product 5.

Like the two ply water soluble product 5 discussed above and for thesame reasons as discussed above, when a third ply 120 is positionedbetween the first ply 10 and second ply 15 it can be practical for theprocess to further comprise the step of positioning the first ply beltside 75 and the second ply belt side 80 to face away from one anotherprior to joining portions of the first ply 10 and second ply 15.

The process can further comprise the step of placing on or in one ormore of the first ply 10, second ply 15, and third ply 120, and anylayer of such ply (e.g. first layer 20, second layer 25, third layer110, fourth layer 115, or any layer constituting the third ply 120) oneither or both the air side or belt side of such ply or continuous plyweb an active agent selected from the group consisting of unencapsulatedor encapsulate perfume, surfactant, enzyme, bleach, chelant,structurant, builder, organic polymeric compound, brightener, hueingagent, suds suppressor, conditioning agent, humectant, alkalinitysystem, pH control system, buffer alkanolamine, insect repellant, haircare agent, hair conditioning agent, skin care agent, sunscreen agent,skin conditioning agent, fabric softener, anti-wrinkling agent,anti-static agent, fabric care stain removal agent, soil release agent,dispersing agent, suds suppressing agent, suds boosting agent, anti-foamagent, fabric refreshing agent, dishwashing agent, hard surface careagent, antimicrobial agent, antibacterial agent, antifungal agent,bleach activating agent, chelating agent, builder, lotion, air careagent, carpet care agent, dye transfer-inhibiting agent, clay soilremoving agent, anti-redeposition agent, polymeric soil release agent,polymeric dispersing agent, alkoxylated polyamine polymer, alkoxylatedpolycarboxylate polymer, amphilic graft copolymer, dissolution aid,buffering system, water-softening agent, water-hardening agent, pHadjusting agent, flocculating agent, effervescent agent, preservative,cosmetic agent, make-up removal agent, lathering agent, deposition aidagent, coacervate-forming agent, clay, thickening agent, latex, silica,drying agent, odor control agent, antiperspirant agent, cooling agent,warming agent, absorbent gel agent, anti-inflammatory agent, dye,pigment, acid, base, liquid treatment active agent, agricultural activeagent, industrial active agent, ingestible active agent, medicinalagent, teeth whitening agent, tooth care agent, mouthwash agent,periodontal gum care agent, dietary agent, vitamin, minerals,water-treatment agent, water clarifying agent, water disinfecting agent,and mixtures thereof. The active agent may be provided as particlesintroduced into the stream for fibrous elements 30 discharged from anyof the die block assemblies 40. The active agent may end up beingpositioned between plies of the product 5, embedded in one or more ofthe plies forming the product 5, or partially embedded in one or more ofthe plies forming the product 5.

The fibrous water-soluble unit dose articles disclosed herein maycomprise several active agents. Preferably, the fibrous water-solubleunit dose article disclosed herein comprises a perfume, where theperfume is positioned between plies of the article 5, embedded in one ormore of the plies forming the product 5, or partially embedded in one ormore of the plies forming the product 5. More preferably, the fibrouswater-soluble unit dose article disclosed herein comprises aconcentrated perfume composition, as described below, which ispositioned between plies of the article 5, embedded in one or more ofthe plies forming the product 5, or partially embedded in one or more ofthe plies forming the product 5.

During the process of manufacturing a product 5, the perfume, preferablya concentrated perfume composition, may be deposited by an active agentapplicator 135 on the upper facing surface 600 of any ply or in any ply,or on and in any ply, or on the air side 72 of any continuous ply web,or in any continuous ply web by an active agent applicator 135. One ormore active agent applicators 135 can be provided on the manufacturingline 140. An active agent applicator 135 can be a nozzle, extruder,sifter, printer, transfer roll, air atomized spray nozzle, hydraulicallyatomized spray nozzle, fluid applicator, extrusion applicator, hotmeltapplicator, ink jet, flexographic printer, gravure printer, offsetgravure, drop on demand ink jet, or any other device suitable fordepositing an active agent onto a ply, especially a moving ply. Activeagent applicators 135 can be positioned over any over any lane or any ofthe plies.

For reasons of practicality, active agents, such as a perfume, e.g., aconcentrated perfume composition, may be placed on or in or on and inthe upwards facing side of any continuous ply web after the continuousply web is positioned to have the desired side facing up. If an activeagent is applied on or in or on and in a continuous ply web before thecontinuous ply web is finally placed in its vertical position of theproduct 5, the active agent might contact the turning bars 77. Thatcould result poor web handling if active agent residue accumulates onthe turning bars 77. For instance, as shown in FIG. 8, the active agentapplicator 135 places active agent on the third continuous ply web 130after the third continuous ply web 130 is positioned on top of the firstcontinuous ply web 60. After the active agent is placed on the thirdcontinuous ply web 130, the second continuous ply web 65 can be place ontop of the third continuous ply web 130 so that the third continuous plyweb 130 is between the first continuous ply web 60 and the secondcontinuous ply web 65.

Optionally, an active agent, such as a perfume, e.g., a concentratedperfume composition, may be placed on or in the first ply air side 90,i.e. the upwards facing surface of the first continuous ply web 60before the third continuous ply web 130 is positioned on top of thefirst continuous ply web 60. As such, when a three ply product 5 isemployed, active agent can be conveniently provided above or below thethird ply 120, on or in the upper facing surface of either side of thethird ply 120, or on or in an inwardly oriented side of the first ply 10or second ply 10. So, for three ply product 5, multiple incompatibleactive agents can be conveniently separated from one another by thethird ply 120.

The process can further comprise the step of providing a solution offilament-forming composition 35. The filament-forming composition 35 canbe passed through one or more die block assemblies 40 comprising aplurality of spinnerets 45 to form a plurality of fibrous elements 30.The plurality of fibrous elements 30 can be deposited onto a belt 50moving in a machine direction MD to form the first ply 10. The first ply10 or first continuous ply web 60 can be cut in the machine direction toform the second ply 15, second continuous ply web 65, third ply 120, andor third continuous ply web 130, as described previously. Optionally,multiple filament-forming compositions may be supplied to a single dieblock assembly 40 or portions thereof or multiple filament-formingcompositions may be supplied to multiple die block assemblies 40.

The first particles 95 and second particles 105 can be introduced intothe stream of fibrous elements 30 before the fibrous elements 30 aredeposited onto a belt 50.

The process illustrated in FIG. 8 can be used to manufacture three plywater soluble products 5 in a continuous process. The continuous processcan be uninterrupted from the step of providing the filament formingcomposition 35 to formation of the water soluble products 5, whether thewater soluble products 5 exist as part of a web of a plurality of watersoluble products joined to one another or are discrete water solubleproducts separated from one another. A benefit of a continuous processis that the ply or continuous ply webs do not need to be stored beforeconverting such materials into water soluble products. Storage of pliesor continuous ply webs that are water soluble can require undueattention to temperature, humidity, and gentle handling to preserve theintegrity of such materials. By continuous process, it is meant that thesteps of the process occur in on a continuous manufacturing line.

At the upstream end of the process, a filament forming composition 35can be provided. The filament forming composition can passed through adie block assembly 40 comprising a plurality of spinnerets 45 to form aplurality of fibrous elements 30. The fibrous elements 30 can bedeposited on a belt 50 moving in a machine direction to form a firstlayer 20. The first layer 20 can then pass beneath another die blockassembly 40 from which a filament forming composition 35 is exitingthrough a plurality of spinnerets 45 to form a plurality of fibrouselements 30. Particles can be inserted into the stream of fibrouselements 30. The fibrous elements 30 and particles can be laid on top ofthe first layer 20 in a second layer 25. Together, the first layer 20and second layer 25 can form the first ply 10 which can be part of thefirst continuous ply web 60.

The first ply 10 can be cut in the machine direction MD into three lanes125 of plies. The center lane can be the first continuous ply web 60.The outer lanes 125 can be the second continuous ply web 65 and thirdcontinuous ply web 130, of which the second ply 15 and third ply 120 canbe part of, respectively. One or more active agent applicators 135 canapply one or more active agents to the second layer 25.

An optional third ply 120 as part of a third continuous ply web 130 canbe lifted from the belt 50 and placed onto the first ply 10 that can bepart of a first continuous ply web 60. Optionally, the third ply 120 orthird continuous ply web 130 can be inverted before placement upon thefirst ply 10 or first continuous ply web 60. Optionally, one or moreactive agent applicators 135 can apply one or more active agents to theair side of third ply 120 or third continuous ply web 130.

A second ply 15 as part of a second continuous ply web 65 can be liftedfrom the belt 50 and placed on top of the third ply 120 or thirdcontinuous ply web 130, if present, or in the absence thereof, on top ofthe first ply 10 or first continuous ply web 60. Optionally, the secondply 15 or second continuous ply web 65 can be inverted before placementupon the third ply 120 or third continuous ply web 130, if present, orin the absence thereof, on top of the first ply 10 or first continuousply web 60.

As shown in FIG. 8, the turning bars 77 can be provided at a first webhandling station 78 and a second web handling station 79. The first webhandling station 78 can be downstream of the die block assembly 40 andupstream of the second web handling station 79. The active agentapplicator or applicators 135 can be positioned upstream of the firstweb handling station 78 and or between the first web handling station 78and the second web handling station 79. The active agent applicator 135can be positioned upstream of the first web handling station 79 andpositioned to overlie the first continuous ply web 60. Optionally, theactive agent applicator 135 can be positioned between the first webhandling station 78 and the second web handling station 79 so that itoverlies the third continuous ply web 130, the first continuous ply web60 incidentally being beneath the third continuous ply web 130.Positioning the active applicator or applicators 135 as such permits theactive agent to be positioned towards the interior of the finishedproduct 5, reducing the potential for the consumer to contact the activeagent.

The water soluble products 5 can be printed upon by one or more printingunits 150. A printing unit 150 can be positioned anywhere on themanufacturing line so that the desired surface of one or more of thefirst ply 10, second ply 15, and or third ply 120 can be printed upon.The printing can be CMYK printing. The printing can be laser jet, inkjet, gravure, pad, rotogravure, flexographic, offset, screen,lithographic, or any other printing approach suitable for printing websof material, particularly process that are best suited for nonwovenmaterials. A drier 220 can be located downstream or upstream of theprinting unit 150.

The first ply 10 and second ply 15, or a first portion 11 of the firstply 10 and a second portion 16 of a second ply 15, can be joined to oneanother, for instance by using a bonding roll, to form the water solubleproduct 5. If there is a third ply 120 between the first ply 10 and thesecond ply 15, the third ply 120 can be contained within the first ply10 and second ply 15. Optionally, the first ply 10 and second ply 15 canbe joined to the third ply 120 so that the first ply 10 and second ply15 are joined to one another through the third ply 120.

Plies can be bonded to one another by thermal bonding. Thermal bondingcan be practical if the plies contain thermoplastic powder, optionallywater soluble thermoplastic material. Thermal bonding can also bepractical if the fibers constituting the plies are thermoplastic. Pliescan optionally be calendar bonded, point bonded, ultrasonically bonded,infrared bonded, through air bonded, needle punched, hydroentangled,melt bonded, adhesive bonded, or other known technical approach forbonding plies of material.

The water soluble products 5 can be separated from one another by a diecutter 160, optionally a rotary die cutter 160. A rotary die cutter 160comprises a die roll and an anvil roll, the die roll and anvil rotatingcounter to one another. The plies can be bonded to one another and diecut in a single step using a single reciprocating bonding and diecutting apparatus or a rotary bonding and die cutting apparatus. In arotary bonding and die cutting apparatus that combines the bonding anddie cutting, the die is shaped to provide a die cut in which thematerial being cut is pinched between the knife-edge of the die and thesmooth surface of the anvil. Further the die is shaped to compressportions of the plies, or continuous ply webs, and layers thereoftogether to bond the plies, continuous ply webs, and layers thereof toone another. The die can be a patterned die that provides a cutting andbonding pattern to the plies, continuous ply webs, and layers thereof.Optionally, the die can be heated, which might be practical for thermalbonding of the plies, continuous ply webs, and layers thereof.

A three ply water soluble product 5 is shown in FIG. 9. Each of theplies can be a multi-layer ply.

There can be intermingling of fibers of one layer with fibers of anotherlayer next thereto. There can also be intermingling of fibers of one plywith fibers of another layer or ply next thereto. As shown in FIG. 9,the third ply 120 can be between the first ply 10 and second ply 15. Thethird ply 120 can be a single layer ply or a multi-layer ply. The thirdply 120 can have a third ply belt side 165 and third ply air side 170opposite the third ply belt side 165. The third ply 120 can comprise afibrous fifth layer 175 and a fibrous sixth layer 180. The fifth layer175 and the sixth layer 180 together forming the third ply 120.Optionally, the third ply 120 can comprise a plurality of thirdparticles 185. Further optionally, the sixth layer 180 can comprisethird particles 185. One or more active agents 190 can be between thethird ply 120 and the second ply 15. The third ply 120 can optionally beflipped relative to that shown in FIG. 9 with sixth layer 165 orientedtowards the second layer 25. Likewise, the plies can be arranged in anydesired order in any desired orientation.

There can be any integer number greater than or equal to two of plies ina product 5. That may be accomplished by providing such number of pliesor continuous ply webs and stacking such plies or continuous ply webs,inverting any of the plies or continuous ply webs as desired, andassembling such plies or continuous ply webs to for such products 5.

Concentrated Perfume Composition

The concentrated perfume composition may comprise a perfume and anoil-binding agent.

The concentrated perfume composition may comprise from about 55% toabout 90% preferably from about 60% to about 85%, more preferably fromabout 65% to about 80%, by weight of the composition, of a perfume. Anincreased concentration of perfume may provide for increased depositionof perfume onto fabrics.

As used herein, the term “perfume” encompasses the perfume raw materials(PRMs) and perfume accords. The term “perfume raw material” as usedherein refers to compounds having a molecular weight of at least about100 g/mol and which are useful in imparting an odor, fragrance, essenceor scent, either alone or with other perfume raw materials. As usedherein, the terms “perfume ingredient” and “perfume raw material” areinterchangeable. The term “accord” as used herein refers to a mixture oftwo or more PRMs.

Non-limiting examples of perfume and perfumery ingredients include, butare not limited to, aldehydes, ketones, esters, and the like. Otherexamples include various natural extracts and essences which cancomprise complex mixtures of ingredients, such as orange oil, lemon oil,rose extract, lavender, musk, patchouli, balsamic essence, sandalwoodoil, pine oil, cedar, and the like. Finished perfumes can compriseextremely complex mixtures of such ingredients.

Typical PRM comprise inter alia alcohols, ketones, aldehydes, esters,ethers, nitrites and alkenes, such as terpene. A listing of common PRMscan be found in various reference sources, for example, “Perfume andFlavor Chemicals”, Vols. I and II; Steffen Arctander Allured Pub. Co.(1994) and “Perfumes: Art, Science and Technology”, Miller, P. M. andLamparsky, D., Blackie Academic and Professional (1994).

The PRMs are characterized by their boiling points (B.P.) measured atthe normal pressure (760 mm Hg), and their octanol/water partitioningcoefficient (P). Based on these characteristics, the PRMS may becategorized as Quadrant I, Quadrant II, Quadrant III, or

Quadrant IV perfumes, as described in more detail below. Octanol/waterpartitioning coefficient of a PRM is the ratio between its equilibriumconcentration in octanol and in water. The log P of many PRMs has beenreported; for example, the Pomona92 database, available from DaylightChemical Information Systems, Inc. (Daylight CIS, Irvine, Calif., USA)contains many, along with citations to the original literature. However,the log P values are most conveniently calculated by the “C LOG P”program, also available from Daylight CIS. This program also listsexperimental log P values when they are available in the Pomona92database. The “calculated log P” (C log P) is determined by the fragmentapproach on Hansch and Leo (cf., A. Leo, in Comprehensive MedicinalChemistry, Vol. 4, C. Hansch, P. G Sammens, J. B. Taylor and C. A.Ransden, Eds., p. 295, Pergamon Press, 1990, incorporated herein byreference). The fragment approach is based on the chemical structure ofeach PRM, and takes into account the numbers and types of atoms, theatom connectivity, and chemical bonding. The C log P values, which arethe most reliable and widely used estimates for this physicochemicalproperty, are preferably used instead of the experimental log P valuesin the selection of PRMs which are useful in the present invention.

The boiling points of many PRMs are given in, e.g., “Perfume and FlavorChemicals (Aroma Chemicals),” S. Arctander, published by the author,1969, incorporated herein by reference. Other boiling point values canbe obtained from different chemistry handbooks and databases, such asthe Beilstein Handbook, Lange's Handbook of Chemistry, and the CRCHandbook of Chemistry and Physics. When a boiling point is given only ata different pressure, usually lower pressure than the normal pressure of760 mm Hg, the boiling point at normal pressure can be approximatelyestimated by using boiling point-pressure nomographs, such as thosegiven in “The Chemist's Companion,” A. J. Gordon and R. A. Ford, JohnWiley & Sons Publishers, 1972, pp. 30-36.

Perfume raw materials having a B.P. lower than 250° C. and a C log Plower than 3.0 are called Quadrant I perfumes. Non-limiting examples ofQuadrant I perfume raw materials include Allyl Caproate, Arnyl Acetate,Arnyl Propionate, Anisic Aldehyde, Anisole, Benzaldehyde, BenzylAcetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl IsoValerate, Benzyl Propionate, Beta Gamma Hexenol, Camphor Gum,laevo-Carveol, d-Carvone, laevo-Carvone, Cinnamic Alcohol, CinnarnylFormate, cis-Jasmone, cis-3-Hexenyl Acetate, Curninic, alcohol, Cuminicaldehyde, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl CarbinylAcetate, Ethyl Acetate, Ethyl Aceto Acetate, Ethyl Amyl Ketone, EthylBenzoate, Ethyl Butyrate, Ethyl Hexyl Ketone, Ethyl Phenyl Acetate,Eucalyptol, Eugenol, Fenchyl Alcohol, Flor Acetate (tricyclo DecenylAcetate), Frutene (tricyclo Decenyl Propionate), Geraniol, Hexenol,Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydratropic Alcohol,Hydroxycitronellal, Isoamyl Alcohol, Isomenthone, Isopulegyl Acetate,Isoquinoline, cis jasmone, Ligustral, Linalool, Linalool Oxide, LinalylFormate, Menthone, Methyl Acetophenone, Methyl Arnyl Ketone, MethylAnthranilate, Methyl Benzoate, Methyl Benzyl Acetate, nerol, phenylethyl alcohol, alpha-terpineol, Propanoic acid ethyl ester, EthylPropionate, Acetic acid 2-methylpropyl ester, Isobutyl Acetate, Butanoicacid 2-methyl-ethyl ester, Ethyl-2-Methyl Butyrate, 2-Hexenal, (E)-,2-Hexena,1 Benzeneacetic acid methyl ester, Methyl Phenyl Acetate,1,3-Dioxolane-2-acetic acid 2-methyl-ethyl ester, Fructone,Benzeneacetaldehyde .alpha.-methyl-, Hydratropic Aldehyde, Acetic acid(2-methylbutoxy)-2-propenyl ester, Allyl Amyl Glycolate, Ethanol2,2′-oxybis-, Calone 161, 2(3H)-Furanone 5-ethyldihydro-, GammaHexalactone, 2H-Pyran 3,6-dihydro-4-methyl-2-(2-methyl-1-propenyl)-,Nerol Oxide, 2-Propenal 3-phenyl-, Cinnamic Aldehyde, 2-Propenoic acid3-phenyl-methyl ester, Methyl Cinnamate, 4H-Pyran-4-one2-ethyl-3-hydroxy-, Ethyl Maltol, 2-Heptanone, Methyl Amyl Ketone,Acetic acid pentyl ester, Iso Amyl-Acetate, Heptenone methyl-, MethylHeptenone, 1-Heptanol, Heptyl Alcohol, 5-Hepten-2-one 6-methyl-, MethylHeptenone, Ethanol 2-(2-methoxyethoxy)-, Veramoss Sps,Tricyclo[2.2.1.02,6]heptane 1-ethyl-3-methoxy-, Neoproxen, Benzene1,4-dimethoxy-, Hydroquinone Dimethyl Ether, Carbonic acid 3-hexenylmethyl ester (Z)—, Liffarome, Oxirane2,2-dimethyl-3-(3-methyl-2,4-pentadienyl)-, Myroxide, Ethanol2-(2-ethoxyethoxy)-, Diethylene Glycol Mono Ethylether,Cyclohexaneethanol, Cyclohexyl Ethyl Alcohol, 3-Octen-1-ol (Z)—, OctenolDix, 3-Cyclohexene-1-carboxaldehyde 3,6-dimethyl-, Cyclovertal,1,3-Oxathiane 2-methyl-4-propyl-cis-, Oxane, Acetic acid 4-methylphenylester, Para Cresyl Acetate, Benzene (2,2-dimethoxyethyl)-, PhenylAcetaldehyde Dimethyl Acetal, Octanal 7-methoxy-3,7-dimethyl-,Methoxycitronellal Pq, 2H-1-Benzopyran-2-one octahydro-, OctahydroCoumarin, Benzenepropanal .beta.-methyl-, Trifemal,4,7-Methano-1H-indenecarboxaldehyde octahydro-, Formyltricyclodecan,Ethanone 1-(4-methoxyphenyl)-, Para Methoxy Acetophenone, Propanenitrile3-(3-hexenyloxy)-(Z)—, Parmanyl, 1,4-Methanonaphthalen-5(1H)-one4,4a,6,7,8,8a-hexahydro-, Tamisone, Benzene [2-(2-propenyloxy)ethyl]-,LRA 220, Benzenepropanol, Phenyl Propyl Alcohol, 1H-Indole, Indole,1,3-Dioxolane 2-(phenylmethyl)-, Ethylene Glycol Acetal/PhenylAcetaldehyde, 2H-1-Benzopyran-2-one 3,4-dihydro-, Dihydrocoumarin, andmixtures thereof.

Perfume raw materials having a B.P. of about 250° C. or higher and a Clog P lower than 3.0 are called Quadrant II perfumes. Non-limitingexamples of Quadrant II perfume raw materials include coumarin, eugenol,iso-eugenol, indole, methyl cinnamate, methyl dihydrojasmonate,methyl-N-methyl anthranilate, beta-methyl naphthyl ketone,delta-Nnonalactone, vanillin, and mixtures thereof.

Perfume raw materials having a B.P. less than 250° C. and a C log Phigher than about 3.0 are called Quadrant III perfumes. Non-limitingexamples of Quadrant III perfume raw materials include iso-bomylacetate, carvacrol, alpha-citronellol, paracymene, dihydro myrcenol,geranyl acetate, d-limonene, linalyl acetate, vertenex.

Perfume raw materials having a B.P. of about 250° C. or higher and a Clog P of about 3.0 or higher are called Quadrant IV perfumes or enduringperfumes. Non-limiting examples of enduring perfume raw materialsinclude allyl cyclohexane propionate, ambrettolide, amyl benzoate, amylcinnamate, amyl cinnamic aldehyde, amyl cinnamic aldehyde dimethylacetal, iso-amyl salicylate, hydroxycitronellal-methyl anthranilate(known as Aurantiol®), benzophenone, benzyl salicylate, para-tert-butylcyclohexyl acetate, iso-butyl quinoline, beta-caryophyllene, cadinene,cedrol, cedryl acetate, cedryl formate, cinnamyl cinnamate, cyclohexylsalicylate, cyclamen aldehyde, dihydro isojasmonate, diphenyl methane,diphenyl oxide, dodecalactone,1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethanone(known as iso E Super®), ethylene brassylate, methyl phenyl glycidate,ethyl undecylenate, 15-hydroxypentadecanoic acid lactone (known asExaltolide®),1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran(known as Galaxolide®), geranyl anthranilate, geranyl phenyl acetate,hexadecanolide, hexenyl salicylate, hexyl cinnamic aldehyde, hexylsalicylate, alpha-irone, gamma-ionone, gamma-n-methyl ionone,para-tertiary-butyl-alpha-methyl hydrocinnamic aldehyde (known asLilial®), lilial (p-t-bucinal)®, linalyl benzoate, 2-methoxynaphthalene, methyl dihydrojasmone, musk indanone, musk ketone, musktibetine, myristicin, oxahexadecanolide-10, oxahexadecanolide-11,patchouli alcohol, 5-acetyl-1,1,2,3,3,6-hexamethylindan (known asPhantolide®), phenyl ethyl benzoate, phenylethylphenylacetate, phenylheptanol, phenyl hexanol, alpha-santalol, delta-undecalactone,gamma-undecalactone, vetiveryl acetate, yara-yara, ylangene.

The perfume raw materials and accords may be obtained from one or moreof the following perfume material suppliers Firmenich (Geneva,Switzerland), Givaudan (Argenteuil, France), IFF (Hazlet, N.J., USA),Quest (Mount Olive, N.J., USA), Bedoukian (Danbury, Conn., USA), SigmaAldrich (St. Louis, Mo., USA), Millennium Specialty Chemicals (OlympiaFields, Ill.), Polarone International (Jersey City, N.J., USA),Fragrance Resources (Keyport, N.J., USA), and Aroma & Flavor Specialties(Danbury, Conn., USA).

The perfume accords may be formulated around “enduring” perfumes(Quadrant IV) due to their high deposition efficiency hence odor impacton fabrics, while “non-enduring” perfumes, especially Quadrant I perfumeingredients, are considered difficult to deposit onto fabrics and assuch typically are used solely in very low amount to minimize waste andpollution. Quadrant I perfume ingredients are hydrophilic (e.g., a C logP lower than 3.0) and have low boiling points (e.g., a B.P. lower than250° C.); thus, they are easily lost to the wash or rinse medium orduring heat drying.

Oil-Binding Agent: Quaternary Ammonium Compound in Concentrated PerfumeComposition

The concentrated perfume composition may comprise an oil-binding agent.The oil-binding agent may be a quaternary ammonium compound. Withoutwishing to be bound by theory, it has been found that the incorporationof a quaternary ammonium compound within the concentrated perfumecompositions may result in favorable ranges of viscosity and onset ofmelt. When favorable ranges of viscosity and onset of melt are reached,the concentrated perfume composition may be in a semi-solid state thatcan be pumped through the machinery and applied to a fibrous ply,without leaking through, deforming, and/or dissolving the fibrous ply.

The concentrated perfume composition may comprise from about 10% toabout 45% preferably from about 15% to about 40% more preferably fromabout 20% to about 35%, by weight of a composition, of a quaternaryammonium compound.

The quaternary ammonium compound may be a quaternary ammonium estercompound. Suitable quaternary ammonium ester compounds include but arenot limited to, materials selected from the group consisting ofmonoester quaternary ammonium compounds, diester quaternary ammoniumcompounds, triester quaternary ammonium compounds and mixtures thereof.The level of monoester quaternary ammonium compound may be from 2.0% to40.0%, the level of diester quaternary ammonium compound may be from40.0% to 98.0%, the level of triester quaternary ammonium compound maybe from 0.0% to 25.0% by weight of total quaternary ammonium estercompound.

The oil-binding agent may be a quaternary ammonium compound selectedfrom the group consisting of diester quaternary ammonium compounds,diethyl ester quaternary ammonium compounds, and mixtures thereof.Preferably, the oil-binding agent is is selected from the groupconsisting of diethylester dimethyl ammonium chloride,bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid esterand isomers thereof, N,N,N-tri(2-hydroxyethyl)-N-methyl ammoniummethylsulfate fatty acid ester, polyglyceryl-6 dipalmitate,N,N-bis(2-hydroxyethyl)-N,N-dimethyl ammonium chloride fatty acid ester,and mixtures thereof.

The quaternary ammonium compound may be a compound of Formula (II):

{R² _((4-m))−N+-[X—Y—R¹]_(m)}A-  Formula (II)

wherein:

-   -   m is 1, 2 or 3;    -   each R¹ is independently hydrocarbyl, or branched hydrocarbyl        group, preferably R¹ is linear, more preferably IV is partially        unsaturated linear alkyl chain;    -   each R² is independently a C₁-C₃ alkyl or hydroxyalkyl group,        preferably R² is selected from methyl, ethyl, propyl,        hydroxyethyl, 2-hydroxypropyl, 1-methyl-2-hydroxyethyl,        poly(C₂₋₃ alkoxy), polyethoxy, benzyl;    -   each X is independently (CH₂)n, CH₂—CH(CH₃)— or CH—(CH₃)—CH₂—        and    -   each n is independently 1, 2, 3 or 4, preferably each n is 2;    -   each Y is independently —O—(O)C— or —C(O)—O—;    -   A- is independently selected from the group consisting of        chloride, methyl sulfate, and ethyl sulfate, preferably A- is        selected from the group consisting of chloride and methyl        sulfate, more preferably A- is methyl sulfate;

with the proviso that when Y is —O—(O)C—, the sum of carbons in each R¹is from 13 to 21, preferably from 13 to 19. It is considered thatcompounds of Formula (II) may have the proviso that the value of each mis identical.

Examples of suitable quaternary ammonium ester compounds are thosecommercially available under the tradenames REWOQUAT®WE 18 andREWOQUAT®WE 20, available from Evonik Industries (Essen, Germany). Otherexamples of suitable quaternary ammonium ester compounds are thosecommercial available under the tradenames STEPANTEX® GA90, STEPANTEX®VK90, and STEPANTEX® VL90A, available from Stepan Company (Northfield,Ill., USA).

The quaternary ammonium compound may have an Iodine Value of from about1 to about 30 (namely, the iodine value of the fatty acyl group of thecompound), preferably from about 1 to about 20. The fatty acid fromwhich the quaternary ammonium compound is derived may comprise fromabout 2.0% to about 20.0%, preferably from about 3.0% to about 15.0%,more preferably from about 4.0% to about 15.0% of double unsaturated C18chains (“C18:2”) by weight of total fatty acid chains.

Hydrophobic Ester

The concentrated perfume composition may optionally comprise ahydrophobic ester. The incorporation of a hydrophobic ester in theconcentrated perfume composition may contribute to favorable ranges ofviscosity and onset of melt. The inclusion of a hydrophobic ester maydecrease the time needed for the concentrated perfume composition toreach the desired viscosity.

The concentrated perfume composition may comprise from about 1% to about10%, preferably from about 1% to about 8%, more preferably from about 1%to about 5% by weight of the composition, of a hydrophobic ester.

The hydrophobic ester may be an alkyl ester. The hydrophobic ester maybe an alkyl ester of Formula (I):

-   -   R₁: linear or branched C12-C22 alkyl    -   R₂: linear or branched C2-C8 alkyl.

Preferably, the hydrophobic ester is selected from the group consistingof isopropyl laureate, isopropyl myristate, isopropyl palmitate, andmixtures thereof. More preferably, the hydrophobic ester may be an alkylester wherein the alkyl ester is isopropyl myristate.

Viscosity and Onset of Melt

The concentrated perfume composition may have a shear viscosity of fromabout 4 Pa-s to about 200 Pa-s, preferably from about 10 Pa-s to about150 Pa-s, more preferably from about 50 Pa-s to about 100 Pa-s whenmeasured at 1 s⁻¹ at 20° C. as determined according to the ShearViscosity Test Method described herein.

The concentrated perfume composition may have a shear viscosity of fromabout 1 Pa-s to about 25 Pa-s, preferably from about 1 Pa-s to about 20Pa-s, more preferably from about 1 Pa-s to about 15 Pa-s when measuredat 10 s⁻¹ at 20° C. as determined according to the Shear Viscosity TestMethod described herein.

The concentrated perfume composition may have an onset of melt of fromabout 5° C. to about 25° C., preferably from about 5° C. to about 20°C., more preferably from about 5° C. to about 15° C. as determinedaccording to the Differential calorimetry Test Method described herein.

It has been found that concentrated perfume compositions having theviscosity ranges and onset of melt ranges of the present disclosure maybe able to be pumped efficiently when applying the composition to afibrous ply, while also being viscous enough to not leak through,deform, or dissolve the fibrous ply. Further, concentrated perfumecompositions having the viscosity ranges and onset of melt ranges of thepresent disclosure may be less likely to migrate within the article. Aconcentrated perfume composition having the viscosity ranges and onsetof melt ranges of the present disclosure may be semi-solid to solid,which tends to inhibit migration of the composition.

Active Agents

The fibrous water-soluble unit dose article may comprise one or moreactive agents other than perfume. The active agents may be present inthe fibrous elements, in the particles, or as a concentrated compositionor slurry in the article.

One or more active agents may be released from the fibrous elementand/or particle and/or fibrous structure when the fibrous element and/orparticle and/or fibrous structure is exposed to a triggering condition.The active agents may be released from the fibrous element and orfibrous structure or part thereof loses its physical structure (e.g.dissolves, melts), alters its physical structure (e.g swells, shrinks,lengthens, shortens). The active agents may be released may be releasedwhen the fibrous structure or part thereof changes in morphology.

The fibrous element and/or particle and/or fibrous structure may releasean active agent upon the fibrous element and/or particle and/or fibrousstructure being exposed to a triggering condition that results in therelease of the active agent, such as by causing the fibrous elementand/or particle and/or fibrous structure to lose or alter its identityas discussed above. Non-limiting examples of triggering conditionsinclude exposing the fibrous element and/or particle and/or fibrousstructure to solvent, a polar solvent, such as alcohol and/or water.and/or a non-polar solvent, which may be sequential, depending uponwhether the filament-forming material comprises a polar solvent-solublematerial and/or a non-polar solvent-soluble material; forming a washliquor by contacting the fibrous structure product with water.

The active agent may be selected from the group consisting of asurfactant, a structurant, a builder, a polymeric dispersing agent, anenzyme, an enzyme stabilizer, a bleach system, a brightener, a hueingagent, a chelating agent, a suds suppressor, a conditioning agent, ahumectant, a perfume, a perfume microcapsule, a filler or carrier, analkalinity system, a pH control system, a buffer, an alkanolamine,mosquito repellant, and mixtures thereof.

Surfactant

The surfactant may be selected from the group consisting of anionicsurfactants, nonionic surfactants, cationic surfactants, zwitterionicsurfactants, amphoteric surfactants, ampholytic surfactants, andmixtures thereof.

Anionic Surfactant

Suitable anionic surfactants may exist in an acid form, and the acidform may be neutralized to form a surfactant salt. Typical agents forneutralization include metal counterion bases, such as hydroxides, e.g.,NaOH or KOH. Further suitable agents for neutralizing anionicsurfactants in their acid forms include ammonia, amines, oralkanolamines Non-limiting examples of alkanolamines includemonoethanolamine, diethanolamine, triethanolamine, and other linear orbranched alkanolamines known in the art; suitable alkanolamines include2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or1-amino-3-propanol. Amine neutralization may be done to a full orpartial extent, e.g., part of the anionic surfactant mix may beneutralized with sodium or potassium and part of the anionic surfactantmix may be neutralized with amines or alkanolamines.

Anionic surfactants may be supplemented with salt as a means to regulatephase behavior; suitable salts may be selected from the group consistingof sodium sulfate, magnesium sulfate, sodium carbonate, sodium citrate,sodium silicate, and mixtures thereof.

Non-limiting examples of suitable anionic surfactants include anyconventional anionic surfactant. This may include a sulfate detersivesurfactant, for e.g., alkoxylated and/or non-alkoxylated alkyl sulfatematerials, and/or sulfonic detersive surfactants, e.g., alkyl benzenesulfonates. Suitable anionic surfactants may be derived from renewableresources, waste, petroleum, or mixtures thereof. Suitable anionicsurfactants may be linear, partially branched, branched, or mixturesthereof.

Alkoxylated alkyl sulfate materials comprise ethoxylated alkyl sulfatesurfactants, also known as alkyl ether sulfates or alkyl polyethoxylatesulfates. Examples of ethoxylated alkyl sulfates include water-solublesalts, particularly the alkali metal, ammonium and alkylolammoniumsalts, of organic sulfuric reaction products having in their molecularstructure an alkyl group containing from about 8 to about 30 carbonatoms and a sulfonic acid and its salts. (Included in the term “alkyl”is the alkyl portion of acyl groups. In some examples, the alkyl groupcontains from about 15 carbon atoms to about 30 carbon atoms. In otherexamples, the alkyl ether sulfate surfactant may be a mixture of alkylether sulfates, said mixture having an average (arithmetic mean) carbonchain length within the range of about 12 to 30 carbon atoms, and insome examples an average carbon chain length of about 12 to 15 carbonatoms, and an average (arithmetic mean) degree of ethoxylation of fromabout 1 mol to 4 mols of ethylene oxide, and in some examples an average(arithmetic mean) degree of ethoxylation of 1.8 mols of ethylene oxide.In further examples, the alkyl ether sulfate surfactant may have acarbon chain length between about 10 carbon atoms to about 18 carbonatoms, and a degree of ethoxylation of from about 1 to about 6 mols ofethylene oxide. In yet further examples, the alkyl ether sulfatesurfactant may contain a peaked ethoxylate distribution.

Non-alkoxylated alkyl sulfates may also be added to the discloseddetergent compositions and used as an anionic surfactant component.Examples of non-alkoxylated, e.g., non-ethoxylated, alkyl sulfatesurfactants include those produced by the sulfation of higher C₈-C₂₀fatty alcohols. In some examples, primary alkyl sulfate surfactants havethe general formula: ROSO₃ ⁻ M⁺, wherein R is typically a linear C₈-C₂₀hydrocarbyl group, which may be straight chain or branched chain, and Mis a water-solubilizing cation. In some examples, R is a C₁₀-C₁₈ alkyl,and M is an alkali metal. In other examples, R is a C₁₂/C₁₄ alkyl and Mis sodium, such as those derived from natural alcohols.

Other useful anionic surfactants can include the alkali metal salts ofalkyl benzene sulfonates, in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain (linear) or branched chainconfiguration. In some examples, the alkyl group is linear. Such linearalkylbenzene sulfonates are known as “LAS.” In other examples, thelinear alkylbenzene sulfonate may have an average number of carbon atomsin the alkyl group of from about 11 to 14. In a specific example, thelinear straight chain alkyl benzene sulfonates may have an averagenumber of carbon atoms in the alkyl group of about 11.8 carbon atoms,which may be abbreviated as C11.8 LAS.

Suitable alkyl benzene sulphonate (LAS) may be obtained, by sulphonatingcommercially available linear alkyl benzene (LAB); suitable LAB includeslow 2-phenyl LAB, such as those supplied by Sasol under the tradenameIsochem® or those supplied by Petresa under the tradename Petrelab®,other suitable LAB include high 2-phenyl LAB, such as those supplied bySasol under the tradename Hyblene®. A suitable anionic detersivesurfactant is alkyl benzene sulphonate that is obtained by DETALcatalyzed process, although other synthesis routes, such as HF, may alsobe suitable. In one aspect a magnesium salt of LAS is used.

Another example of a suitable alkyl benzene sulfonate is a modified LAS(MLAS), which is a positional isomer that contains a branch, e.g., amethyl branch, where the aromatic ring is attached to the 2 or 3position of the alkyl chain.

The anionic surfactant may include a 2-alkyl branched primary alkylsulfates have 100% branching at the C2 position (C1 is the carbon atomcovalently attached to the alkoxylated sulfate moiety). 2-alkyl branchedalkyl sulfates and 2-alkyl branched alkyl alkoxy sulfates are generallyderived from 2-alkyl branched alcohols (as hydrophobes). 2-alkylbranched alcohols, e.g., 2-alkyl-1-alkanols or 2-alkyl primary alcohols,which are derived from the oxo process, are commercially available fromSasol, e.g., LIAL®, ISALCHEM® (which is prepared from LIAL® alcohols bya fractionation process). C14/C15 branched primary alkyl sulfate arealso commercially available, e.g., namely LIAL® 145 sulfate.

The anionic surfactant may include a mid-chain branched anionicsurfactant, e.g., a mid-chain branched anionic detersive surfactant,such as, a mid-chain branched alkyl sulphate and/or a mid-chain branchedalkyl benzene sulphonate.

Additional suitable anionic surfactants include methyl ester sulfonates,paraffin sulfonates, α-olefin sulfonates, and internal olefinsulfonates.

Nonionic Surfactant

Suitable nonionic surfactants include alkoxylated fatty alcohols. Thenonionic surfactant may be selected from ethoxylated alcohols andethoxylated alkyl phenols of the formula R(OC₂H₄)_(n)OH, wherein R isselected from the group consisting of aliphatic hydrocarbon radicalscontaining from about 8 to about 15 carbon atoms and alkyl phenylradicals in which the alkyl groups contain from about 8 to about 12carbon atoms, and the average value of n is from about 5 to about 15.

Other non-limiting examples of nonionic surfactants useful hereininclude: Cs-Cis alkyl ethoxylates, such as, NEODOL® nonionic surfactantsfrom Shell; C₆-C₁₂ alkyl phenol alkoxylates where the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units, or a mixture thereof;C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C₁₄-C₂₂ mid-chain branched alcohols, BA; C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x is from 1 to 30;alkylpolysaccharides; specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants.

Suitable nonionic detersive surfactants also include alkyl polyglucosideand alkyl alkoxylated alcohol. Suitable nonionic surfactants alsoinclude those sold under the tradename Lutensol® from BASF.

Cationic Surfactant

Non-limiting examples of cationic surfactants include: the quaternaryammonium surfactants, which can have up to 26 carbon atoms include:alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethylquaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride;polyamine cationic surfactants; cationic ester surfactants; and aminosurfactants, e.g., amido propyldimethyl amine (APA).

Suitable cationic detersive surfactants also include alkyl pyridiniumcompounds, alkyl quaternary ammonium compounds, alkyl quaternaryphosphonium compounds, alkyl ternary sulphonium compounds, and mixturesthereof.

Suitable cationic detersive surfactants are quaternary ammoniumcompounds having the general formula:

(R)(R₁)(R₂)(R₃)N⁺X⁻

wherein, R is a linear or branched, substituted or unsubstituted C₆₋₁₈alkyl or alkenyl moiety, R₁ and R₂ are independently selected frommethyl or ethyl moieties, R₃ is a hydroxyl, hydroxymethyl or ahydroxyethyl moiety, X is an anion which provides charge neutrality,suitable anions include: halides, for example chloride; sulphate; andsulphonate. Suitable cationic detersive surfactants are mono-C₆₋₁₈ alkylmono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highlysuitable cationic detersive surfactants are mono-C₈₋₁₀ alkylmono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C₁₀₋₁₂alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride andmono-C₁₀ alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.

Zwitterionic Surfactant

Suitable zwitterionic surfactants include: derivatives of secondary andtertiary amines, derivatives of heterocyclic secondary and tertiaryamines, or derivatives of quaternary ammonium, quaternary phosphonium ortertiary sulfonium compounds. Suitable examples of zwitterionicsurfactants include betaines, including alkyl dimethyl betaine andcocodimethyl amidopropyl betaine, C₈ to C₁₈ (for example from C₁₂ toC₁₈) amine oxides, and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group canbe C₈ to C₁₈.

Amphoteric Surfactant

Suitable amphoteric surfactants include aliphatic derivatives ofsecondary or tertiary amines, or aliphatic derivatives of heterocyclicsecondary and tertiary amines in which the aliphatic radical may bestraight or branched-chain and where one of the aliphatic substituentscontains at least about 8 carbon atoms, or from about 8 to about 18carbon atoms, and at least one of the aliphatic substituents contains ananionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.Suitable amphoteric surfactants also include sarcosinates, glycinates,taurinates, and mixtures thereof.

Enzymes

Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, mannanases, pectatelyases, keratinases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases,malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase,laccase, and amylases, or mixtures thereof. A typical combination is anenzyme cocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in a detergent composition, theaforementioned additional enzymes may be present at levels from about0.00001% to about 2%, from about 0.0001% to about 1% or even from about0.001% to about 0.5% enzyme protein by weight of the composition. Thecompositions disclosed herein may comprise from about 0.001% to about 1%by weight of an enzyme (as an adjunct), which may be selected from thegroup consisting of lipase, amylase, protease, mannanase, cellulase,pectinase, and mixtures thereof.

Builders

Suitable builders include aluminosilicates (e.g., zeolite builders, suchas zeolite A, zeolite P, and zeolite MAP), silicates, phosphates, suchas polyphosphates (e.g., sodium tri-polyphosphate), especially sodiumsalts thereof; carbonates, bicarbonates, sesquicarbonates, and carbonateminerals other than sodium carbonate or sesquicarbonate; organic mono-,di-, tri-, and tetracarboxylates, especially water-soluble nonsurfactantcarboxylates in acid, sodium, potassium or alkanolammonium salt form, aswell as oligomeric or water-soluble low molecular weight polymercarboxylates including aliphatic and aromatic types; and phytic acid.Additional suitable builders may be selected from citric acid, lacticacid, fatty acid, polycarboxylate builders, for example, copolymers ofacrylic acid, copolymers of acrylic acid and maleic acid, and copolymersof acrylic acid and/or maleic acid, and other suitable ethylenicmonomers with various types of additional functionalities.Alternatively, the composition may be substantially free of builder.

Polymeric Dispersing Agents

Suitable polymeric dispersing agents include carboxymethylcellulose,poly(vinyl-pyrrolidone), poly (ethylene glycol), an ethyleneoxide-propylene oxide-ethylene oxide (EOx₁POyEOx₂) triblock copolymer,where each of x₁ and x₂ is in the range of about 2 to about 140 and y isin the range of from about 15 to about 70, poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates suchas polyacrylates, maleic/acrylic acid copolymers and laurylmethacrylate/acrylic acid co-polymers.

Suitable polymeric dispersing agents include amphiphilic cleaningpolymers such as the compound having the following general structure:bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof.

Suitable polymeric dispersing agents include amphiphilic alkoxylatedgrease cleaning polymers which have balanced hydrophilic and hydrophobicproperties such that they remove grease particles from fabrics andsurfaces. The amphiphilic alkoxylated grease cleaning polymers maycomprise a core structure and a plurality of alkoxylate groups attachedto that core structure. These may comprise alkoxylatedpolyalkylenimines, for example, having an inner polyethylene oxide blockand an outer polypropylene oxide block. Such compounds may include, butare not limited to, ethoxylated polyethyleneimine, ethoxylatedhexamethylene diamine, and sulfated versions thereof. Polypropoxylatedderivatives may also be included. A wide variety of amines andpolyalklyeneimines can be alkoxylated to various degrees. A usefulexample is 600 g/mol polyethyleneimine core ethoxylated to 20 EO groupsper NH and is available from BASF. The detergent compositions describedherein may comprise from about 0.1% to about 10%, and in some examples,from about 0.1% to about 8%, and in other examples, from about 0.1% toabout 6%, by weight of the detergent composition, of alkoxylatedpolyamines.

Suitable polymeric dispersing agents include carboxylate polymer.Suitable carboxylate polymers, which may optionally be sulfonated,include a maleate/acrylate random copolymer or a poly(meth)acrylatehomopolymer. In one aspect, the carboxylate polymer is apoly(meth)acrylate homopolymer having a molecular weight from 4,000 Dato 9,000 Da, or from 6,000 Da to 9,000 Da.

Suitable polymeric dispersing agents include alkoxylatedpolycarboxylates, which may also be used to provide grease removal.Chemically, these materials comprise poly(meth)acrylates having oneethoxy side-chain per every 7-8 (meth)acrylate units. The side-chainsare of the formula —(CH₂CH₂O)_(m) (CH₂)_(n)CH₃ wherein m is 2-3 and n is6-12. The side-chains are ester-linked to the polyacrylate “backbone” toprovide a “comb” polymer type structure. The molecular weight can vary,but may be in the range of about 2000 to about 50,000. The detergentcompositions described herein may comprise from about 0.1% to about 10%,and in some examples, from about 0.25% to about 5%, and in otherexamples, from about 0.3% to about 2%, by weight of the detergentcomposition, of alkoxylated polycarboxylates.

Suitable polymeric dispersing agents include amphiphilic graftco-polymers. A suitable amphiphilic graft co-polymer comprises (i) apolyethyelene glycol backbone; and (ii) and at least one pendant moietyselected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof.A suitable amphilic graft co-polymer is Sokalan® HP22, supplied fromBASF. Suitable polymers include random graft copolymers, for example, apolyvinyl acetate grafted polyethylene oxide copolymer having apolyethylene oxide backbone and multiple polyvinyl acetate side chains.The molecular weight of the polyethylene oxide backbone is typicallyabout 6000 and the weight ratio of the polyethylene oxide to polyvinylacetate is about 40 to 60 and no more than 1 grafting point per 50ethylene oxide units.

Soil Release Polymer

Suitable soil release polymers have a structure as defined by one of thefollowing structures (I), (II) or (III):

—[(OCHR¹—CHR²)_(n)—O—OC—Ar—CO—]_(d)  (I)

—[(OCHR³—CHR⁴)_(b)—O—OC-sAr—CO—]_(e)  (II)

—[(OCHR⁵—CHR⁶)_(c)—OR⁷]_(f)  (III)

wherein:

a, b and c are from 1 to 200;

d, e and f are from 1 to 50;

Ar is a 1,4-substituted phenylene;

sAr is 1,3-substituted phenylene substituted in position 5 with SO₃Me;

Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or mixtures thereof;

R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; and

R⁷ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀aryl group, or a C₆-C₃₀ arylalkyl group.

Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN300 and SRN325 supplied by Clariant. Other suitable soil releasepolymers are Marloquest polymers, such as Marloquest SL supplied bySasol.

Cellulosic Polymer

Suitable cellulosic polymers including those selected from alkylcellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkylcarboxyalkyl cellulose. The cellulosic polymers may be selected from thegroup consisting of carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixturesthereof. In one aspect, the carboxymethyl cellulose has a degree ofcarboxymethyl substitution from 0.5 to 0.9 and a molecular weight from100,000 Da to 300,000 Da.

Amines

Non-limiting examples of amines may include, but are not limited to,polyetheramines, polyamines, oligoamines, triamines, diamines,pentamines, tetraamines, or combinations thereof. Specific examples ofsuitable additional amines include tetraethylenepentamine,triethylenetetraamine, diethylenetriamine, or a mixture thereof.

Bleaching Agents

Suitable bleaching agents other than bleaching catalysts includephotobleaches, bleach activators, hydrogen peroxide, sources of hydrogenperoxide, pre-formed peracids and mixtures thereof. In general, when ableaching agent is used, the detergent compositions of the presentinvention may comprise from about 0.1% to about 50% or even from about0.1% to about 25% bleaching agent by weight of the detergentcomposition.

Bleach Catalysts

Suitable bleach catalysts include, but are not limited to: iminiumcations and polyions; iminium zwitterions; modified amines; modifiedamine oxides; N-sulphonyl imines; N-phosphonyl imines; N-acyl imines;thiadiazole dioxides; perfluoroimines; cyclic sugar ketones and mixturesthereof.

Brighteners

Commercial fluorescent brighteners suitable for the present disclosurecan be classified into subgroups, including but not limited to:derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylicacid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents.

The fluorescent brightener may be selected from the group consisting ofdisodium4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate(brightener 15, commercially available under the tradename TinopalAMS-GX by BASF),disodium4,4′-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl]-amino}-2,2′-stilbenedisulonate(commercially available under the tradename Tinopal UNPA-GX by BASF),disodium4,4′-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl]-amino}-2,2′-stilbenedisulfonate(commercially available under the tradename Tinopal SBM-GX by BASF).More preferably, the fluorescent brightener is disodium4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate.

The brighteners may be added in particulate form or as a premix with asuitable solvent, for example nonionic surfactant, propanediol.

Fabric Hueing Agents

A fabric hueing agent (sometimes referred to as shading, bluing orwhitening agents) typically provides a blue or violet shade to fabric.Hueing agents can be used either alone or in combination to create aspecific shade of hueing and/or to shade different fabric types. Thismay be provided for example by mixing a red and green-blue dye to yielda blue or violet shade. Hueing agents may be selected from any knownchemical class of dye, including but not limited to acridine,anthraquinone (including polycyclic quinones), azine, azo (e.g.,monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallizedazo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine,diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids,methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine,phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane,triphenylmethane, xanthenes and mixtures thereof.

Suitable fabric hueing agents include dyes, dye-clay conjugates, andorganic and inorganic pigments. Suitable dyes also include smallmolecule dyes and polymeric dyes. Suitable small molecule dyes includesmall molecule dyes selected from the group consisting of dyes fallinginto the Colour Index (C.I.) classifications of Direct, Basic, Reactiveor hydrolysed Reactive, Solvent or Disperse dyes for example that areclassified as Blue, Violet, Red, Green or Black, and provide the desiredshade either alone or in combination. Suitable polymeric dyes includepolymeric dyes selected from the group consisting of polymers containingcovalently bound (sometimes referred to as conjugated) chromogens,(dye-polymer conjugates), for example polymers with chromogensco-polymerized into the backbone of the polymer and mixtures thereof.Suitable polymeric dyes also include polymeric dyes selected from thegroup consisting of fabric-substantive colorants sold under the name ofLiquitint® (Milliken, Spartanburg, S.C. , USA), dye-polymer conjugatesformed from at least one reactive dye and a polymer selected from thegroup consisting of polymers comprising a moiety selected from the groupconsisting of a hydroxyl moiety, a primary amine moiety, a secondaryamine moiety, a thiol moiety and mixtures thereof. Suitable polymericdyes also include polymeric dyes selected from the group consisting ofLiquitint® Violet CT, carboxymethyl cellulose (CMC) covalently bound toa reactive blue, reactive violet or reactive red dye such as CMCconjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow,Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC,alkoxylated triphenyl-methane polymeric colourants, alkoxylatedthiophene polymeric colourants, and mixtures thereof.

The aforementioned fabric hueing agents can be used in combination (anymixture of fabric hueing agents can be used).

Encapsulates

An encapsulate may comprise a core, a shell having an inner and outersurface, said shell encapsulating said core. The core may comprise anylaundry care adjunct, though typically the core may comprise materialselected from the group consisting of perfumes; brighteners; hueingdyes; insect repellants; silicones; waxes; flavors; vitamins; fabricsoftening agents; skin care agents in one aspect, paraffins; enzymes;anti-bacterial agents; bleaches; sensates; and mixtures thereof; andsaid shell may comprise a material selected from the group consisting ofpolyethylenes; polyamides; polyvinylalcohols, optionally containingother co-monomers; polystyrenes; polyisoprenes; polycarbonates;polyesters; polyacrylates; aminoplasts, in one aspect said aminoplastmay comprise a polyureas, polyurethane, and/or polyureaurethane, in oneaspect said polyurea may comprise polyoxymethyleneurea and/or melamineformaldehyde; polyolefins; polysaccharides, in one aspect saidpolysaccharide may comprise alginate and/or chitosan; gelatin; shellac;epoxy resins; vinyl polymers; water insoluble inorganics; silicone; andmixtures thereof.

Preferred encapsulates comprise perfume. Preferred encapsulates comprisea shell which may comprise melamine formaldehyde and/or cross linkedmelamine formaldehyde. Other preferred capsules comprise a polyacrylatebased shell. Preferred encapsulates comprise a core material and ashell, said shell at least partially surrounding said core material, isdisclosed. At least 75%, 85% or even 90% of said encapsulates may have afracture strength of from 0.2 MPa to 10 MPa, and a benefit agent leakageof from 0% to 20%, or even less than 10% or 5% based on total initialencapsulated benefit agent. Preferred are those in which at least 75%,85% or even 90% of said encapsulates may have (i) a particle size offrom 1 microns to 80 microns, 5 microns to 60 microns, from 10 micronsto 50 microns, or even from 15 microns to 40 microns, and/or (ii) atleast 75%, 85% or even 90% of said encapsulates may have a particle wallthickness of from 30 nm to 250 nm, from 80 nm to 180 nm, or even from100 nm to 160 nm. Formaldehyde scavengers may be employed with theencapsulates, for example, in a capsule slurry and/or added to acomposition before, during or after the encapsulates are added to suchcomposition.

Suitable capsules that can be made using known processes. Alternatively,suitable capsules can be purchased from Encapsys LLC of Appleton, Wis.USA. In a preferred aspect the composition may comprise a depositionaid, preferably in addition to encapsulates. Preferred deposition aidsare selected from the group consisting of cationic and nonionicpolymers. Suitable polymers include cationic starches, cationichydroxyethylcellulose, polyvinylformaldehyde, locust bean gum, mannans,xyloglucans, tamarind gum, polyethyleneterephthalate and polymerscontaining dimethylaminoethyl methacrylate, optionally with one or moremonomers selected from the group comprising acrylic acid and acrylamide.

Dye Transfer Inhibiting Agents

Dye transfer inhibiting agents are effective for inhibiting the transferof dyes from one fabric to another during the cleaning process.Generally, such dye transfer inhibiting agents may include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents may be used ata concentration of about 0.0001% to about 10%, by weight of thecomposition, in some examples, from about 0.01% to about 5%, by weightof the composition, and in other examples, from about 0.05% to about 2%by weight of the composition.

Chelating Agents

Suitable chelating agents include copper, iron and/or manganesechelating agents and mixtures thereof. Such chelating agents can beselected from the group consisting of phosphonates, amino carboxylates,amino phosphonates, succinates, polyfunctionally-substituted aromaticchelating agents, 2-pyridinol-N-oxide compounds, hydroxamic acids,carboxymethyl inulins and mixtures thereof. Chelating agents can bepresent in the acid or salt form including alkali metal, ammonium, andsubstituted ammonium salts thereof, and mixtures thereof. Other suitablechelating agents for use herein are the commercial DEQUEST series, andchelants from Monsanto, Akzo-Nobel, DuPont, Dow, the Trilon® series fromBASF and Nalco.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the water-soluble unit dose articles. Suds suppressioncan be of particular importance in the so-called “high concentrationcleaning process” and in front-loading style washing machines. Examplesof suds supressors include monocarboxylic fatty acid and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols.

Additional suitable antifoams are those derived from phenylpropylmethylsubstituted polysiloxanes.

The detergent composition may comprise a suds suppressor selected fromorganomodified silicone polymers with aryl or alkylaryl substituentscombined with silicone resin and a primary filler, which is modifiedsilica. The detergent compositions may comprise from about 0.001% toabout 4.0%, by weight of the composition, of such a suds suppressor.

The detergent composition comprises a suds suppressor selected from: a)mixtures of from about 80 to about 92% ethylmethyl,methyl(2-phenylpropyl) siloxane; from about 5 to about 14% MQ resin inoctyl stearate; and from about 3 to about 7% modified silica; b)mixtures of from about 78 to about 92% ethylmethyl,methyl(2-phenylpropyl) siloxane; from about 3 to about 10% MQ resin inoctyl stearate; from about 4 to about 12% modified silica; or c)mixtures thereof, where the percentages are by weight of the anti-foam.

Suds Boosters

If high sudsing is desired, suds boosters such as the C₁₀-C₁₆alkanolamides may be used. Some examples include the C₁₀-C₁₄ monoethanoland diethanol amides. If desired, water-soluble magnesium and/or calciumsalts such as MgCl₂, MgSO₄, CaCl₂), CaSO₄, and the like, may be added atlevels of about 0.1% to about 2% by weight of the detergent composition,to provide additional suds and to enhance grease removal performance.

Conditioning Agents

Suitable conditioning agents include high melting point fatty compounds.The high melting point fatty compound useful herein has a melting pointof 25° C. or higher, and is selected from the group consisting of fattyalcohols, fatty acids, fatty alcohol derivatives, fatty acidderivatives, and mixtures thereof. Suitable conditioning agents alsoinclude nonionic polymers and conditioning oils, such as hydrocarbonoils, polyolefins, and fatty esters.

Suitable conditioning agents include those conditioning agentscharacterized generally as silicones (e.g., silicone oils, polyoils,cationic silicones, silicone gums, high refractive silicones, andsilicone resins), organic conditioning oils (e.g., hydrocarbon oils,polyolefins, and fatty esters) or combinations thereof, or thoseconditioning agents which otherwise form liquid, dispersed particles inthe aqueous surfactant matrix herein.

Fabric Enhancement Polymers

Suitable fabric enhancement polymers are typically cationically chargedand/or have a high molecular weight. The fabric enhancement polymers maybe a homopolymer or be formed from two or more types of monomers. Themonomer weight of the polymer will generally be between 5,000 and10,000,000, typically at least 10,000 and preferably in the range100,000 to 2,000,000. Preferred fabric enhancement polymers will havecationic charge densities of at least 0.2 meq/gm, preferably at least0.25 meq/gm, more preferably at least 0.3 meq/gm, but also preferablyless than 5 meq/gm, more preferably less than 3 meq/gm, and mostpreferably less than 2 meq/gm at the pH of intended use of thecomposition, which pH will generally range from pH 3 to pH 9, preferablybetween pH 4 and pH 8. The fabric enhancement polymers may be of naturalor synthetic origin.

Pearlescent Agent

Non-limiting examples of pearlescent agents include: mica; titaniumdioxide coated mica; bismuth oxychloride; fish scales; mono and diestersof alkylene glycol. The pearlescent agent may beethyleneglycoldistearate (EGDS).

Hygiene and Malodour

Suitable hygiene and malodor active agents include zinc ricinoleate,thymol, quaternary ammonium salts such as Bardac®, polyethylenimines(such as Lupasol® from BASF) and zinc complexes thereof, silver andsilver compounds, especially those designed to slowly release Ag⁺ ornano-silver dispersions.

Buffer System

The water-soluble unit dose articles described herein may be formulatedsuch that, during use in aqueous cleaning operations, the wash waterwill have a pH of between about 7.0 and about 12, and in some examples,between about 7.0 and about 11. Techniques for controlling pH atrecommended usage levels include the use of buffers, alkalis, or acids,and are well known to those skilled in the art. These include, but arenot limited to, the use of sodium carbonate, citric acid or sodiumcitrate, lactic acid or lactate, monoethanol amine or other amines,boric acid or borates, and other pH-adjusting compounds well known inthe art.

The detergent compositions herein may comprise dynamic in-wash pHprofiles. Such detergent compositions may use wax-covered citric acidparticles in conjunction with other pH control agents such that (i)about 3 minutes after contact with water, the pH of the wash liquor isgreater than 10; (ii) about 10 minutes after contact with water, the pHof the wash liquor is less than 9.5; (iii) about 20 minutes aftercontact with water, the pH of the wash liquor is less than 9.0; and (iv)optionally, wherein, the equilibrium pH of the wash liquor is in therange of from about 7.0 to about 8.5.

Particles

The water-soluble unit dose article disclosed herein may comprise one ormore particles within or on the fibrous structure. The particles may bewater-soluble. The particles may contain soluble and/or insolublematerial, where the insoluble material is dispersible in aqueous washconditions to a suspension mean particle size that is less than about 20microns. The particles may be water-soluble, e.g., substantially free ofinsoluble material.

The particle may be discrete. As used herein, the term “discrete” refersto particles that are structurally distinctive from each other eitherunder naked human eyes or under electronic imaging devices, such asscanning electron microscope (SEM) and transmission electron microscope(TEM). The particles may be discrete from each other under naked humaneyes.

As used herein, the term “particle” refers to a solid matter of minutequantity. The particle may be a powder, granule, agglomerate,encapsulate, microcapsule, and/or prill. The particle may be made usinga number of well known methods in the art, such as spray-drying,agglomeration, extrusion, prilling, encapsulation, pastillation andcombinations thereof. The shape of the particle can be in the form ofspheres, rods, plates, tubes, squares, rectangles, discs, stars, orflakes of regular or irregular shapes. The particles disclosed hereinare generally non-fibrous.

Each of the particles may contain a surfactant having a relatively highhydrophilicity. Such surfactants are very effective in cleaning fabricsand removing stains and are therefore desirable to include inwater-soluble unit dose articles disclosed herein. However, surfactantsof higher hydrophilicity may form a viscous, gel-like hexagonal phasewhile being dissolved in water. It is therefore difficult to formulatesuch surfactants into the above-mentioned fibrous elements, because theviscous hexagonal phase may adversely affect processing of the fibrouselements and formation of the fibrous structure. By formulating suchsurfactants into particles that are distributed throughout the fibrousstructure, such processing challenges can be readily avoided. Further,because the viscous hexagonal phase may slow down dissolution of thewater-soluble unit dose articles in water during use, it is also helpfulto formulate the such hydrophilic surfactants into particles that can beeasily dispersed in water, which improves overall dissolution of thewater-soluble unit dose articles during wash.

The particles may have a relatively low water/moisture content (e.g., nomore than about 10 wt % of total water/moisture, or no more than about 8wt % of total water/moisture, or no more than about 5 wt % of totalmoisture), especially a relatively low free/unbound water content (e.g.,no more than about 3 wt % of free or unbound water, or no more thanabout 1 wt % of free or unbound water), so that water from the particleswill not compromise the structural integrity of the fibrous structure.Further, a controlled moisture content in the particles reduces the riskof gelling in the particles themselves. The water/moisture contentpresent in a particle is measured using the following Water Content TestMethod.

The bulk density of the particles may range from about 500 g/L to about1000 g/L, or from about 600 g/L to about 900 g/L, or from about 700 g/Lto about 800 g/L.

Like the fibrous structures and fibrous elements described hereinabove,the particles of are also characterized by a sufficiently highsurfactant content, e.g., at least about 30%, or at least about 50%, orat least about 60%, and or at least about 70%, by total weight of eachparticle.

Each of the particles may contain a surfactant selected from the groupconsisting of C6-C20 linear or branched alkylalkoxylated sulfates (AAS)having a weight average degree of alkoxylation ranging from about 0.1 toabout 10, C6-C20 alkylalkoxylated alcohols (AA) having a weight averagedegree of alkoxylation ranging from about 5 to about 15, andcombinations thereof. The surfactant may be a C₆-C₂₀ linear or branchedAAS surfactant having a weight average degree of alkoxylation rangingfrom about 0.1 to about 10, or a C₁₀-C₁₆ linear or branchedalkylethoxylated sulfate (AES) having a weight average degree ofalkoxylation ranging from about 1 to about 5. Such AAS (e.g., AES)surfactant can be used either alone or in combination with othersurfactants. The AAS (e.g., AES) surfactant may be used as a mainsurfactant in each particle, i.e., it is present at an amount that is50% or more by total weight of all surfactants in the particle, whileone or more other surfactants (anionic, nonionic, amphoteric, and/orcationic) may be present as co-surfactants for such AAS (e.g., AES). Theparticle may comprise from about 15 wt % to about 60 wt %, or from 20 wt% to 40 wt % alkylalkoxylated sulfate, or from 30 wt % to 80 wt % oreven from 50 wt % to 70 wt % alkylalkoxylated sulfate.

The surfactant in the particles may be a nonionic surfactant. Suitablenonionic surfactants include alkylalkoxylated alcohols, such asalkylethoxylated alcohols and alkylethoxylated phenols of the formulaR(OC₂H₄)—OH, where R is selected from the group consisting of aliphatichydrocarbon radicals containing from about 8 to about 15 carbon atomsand alkyl phenyl radicals in which the alkyl groups contain from about 8to about 12 carbon atoms, and the average value of n is from about 5 toabout 15. The nonionic surfactant may be selected from ethoxylatedalcohols having an average of about 12-14 carbon atoms in the alcoholand an average degree of ethoxylation of about 9 moles of ethylene oxideper mole of alcohol. Other non-limiting examples of nonionic surfactantsuseful herein include: C₈-C₁₈ alkylethoxylates, such as, NEODOL®nonionic surfactants from Shell; C₆-C₁₂ alkyl phenol alkoxylates wherethe alkoxylate units may be ethyleneoxy units, propyleneoxy units, or amixture thereof; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensateswith ethylene oxide/propylene oxide block polymers such as Pluronic®from BASF; C₁₄-C₂₂ mid-chain branched alcohols; C₁₄-C₂₂ mid-chainbranched alkylalkoxylates, BAE_(x), wherein x is from 1 to 30;alkylpolysaccharides, and specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants. Suitable nonionic surfactants also include those sold underthe tradename Lutensol® from BASF.

The nonionic surfactant may be C₆-C₂₀ alkylalkoxylated alcohols (AA)having a weight average degree of alkoxylation ranging from 5 to 15,which may be present in the particles either alone or in combinationwith the AAS or AES surfactant described hereinabove. AA can either bepresent as a main surfactant or as a co-surfactant for AAS or AES in theparticles. An AAS (e.g., AES) surfactant may be present as a mainsurfactant in the particles, while an AA surfactant is present as aco-surfactant for such AAS or AES surfactant, for example, in a weightratio ranging from about 1:15 to about 1:2, or from about 1:10 to about1:3, and or from about 1:8 to about 1:4.

The hydrophilic surfactant may be present in each of the particles in anamount ranging from about 20% to about 90%, or from about 30% to about90%, or from about 40% to about 90%, or from about 50% to about 90%, bytotal weight of each particle.

In addition, the particles described herein may comprise one or moreadditional surfactants selected from the group consisting of otheranionic surfactants (i.e., other than AAS and AES), amphotericsurfactants, cationic surfactants, and combinations thereof, asdescribed hereinabove for the fibrous structure. Such additionalsurfactant(s) may be present in each of the particles in an amountranging from about 0% to about 50%, or from about 1% to about 40%, orfrom about 2% to about 30%, or from about 5% to about 20%, by totalweight of each particle. For example, such additional surfactant(s) maybe an anionic surfactant selected from the group consisting of C₆-C₂₀linear or branched LAS, C₆-C₂₀ linear or branched AS, C₆-C₂₀ linear orbranched alkyl sulfonates, C₆-C₂₀ linear or branched alkyl carboxylates,C₆-C₂₀ linear or branched alkyl phosphates, C₆-C₂₀ linear or branchedalkyl phosphonates, C₆-C₂₀ alkyl N-methyl glucose amides, C₆-C₂₀ methylester sulfonates (MES), and combinations thereof. The particle maycomprise alkylbenzene sulfonate, for example, linear alkylbenzenesulfonate (LAS). The particle may comprise from 1 wt % to 50 wt %alkylbenzene sulfonate, or from 5 wt % to 30 wt % alkylbenzenesulfonate.

The above-mentioned surfactant(s) may form a surfactant system, whichcan be present in an amount ranging from about 5% to about 90%, or fromabout 10% to about 90%, or from about 20% to about 90%, or from about30% to about 90%, and or from about 50% to about 90%, by total weight ofthe particles.

The particles described herein may comprise one or more additionalactive agents (in addition to surfactant as described hereinabove).

Each of the particles may further comprise from about 0.5% to about 20%,or from about 1% to about 15%, or from about 2% to about 10% by totalweight of such particle of a rheology modifier. As used herein, the term“rheology modifier” means a material that interacts with concentratedsurfactants, preferably concentrated surfactants having a mesomorphicphase structure, in a way that substantially reduces the viscosity andelasticity of said concentrated surfactant. Suitable rheology modifiersinclude, but are not limited to, sorbitol ethoxylate, glycerolethoxylate, sorbitan esters, tallow alkyl ethoxylated alcohol, ethyleneoxide-propylene oxide-ethylene oxide (EOx₁POyEOx₂) triblock copolymerswherein each of x₁ and x₂ is in the range of about 2 to about 140 and yis in the range of from about 15 to about 70, polyethyleneimine (PEI),alkoxylated variants of PEI, and preferably ethoxylated PEI,N,N,N′,N′-tetraethoxylethylenediamine, and mixtures thereof.

The rheology modifier is preferably a “functional rheology modifier,”which means the rheology modifier has additional detergentfunctionality. In some cases, a dispersant polymer, described hereinbelow, may also function as a functional rheology modifier. The rheologymodifier is preferably selected from the group consisting of analkoxylated polyalkyleneimine, an ethylene oxide-propyleneoxide-ethylene oxide (EOx₁POyEOx₂) triblock copolymer wherein each of x₁and x₂ is in the range of about 2 to about 140 and y is in the range offrom about 15 to about 70, an N,N,N′,N′-tetraethoxylethylenediamine, andmixtures thereof.

The rheology modifier may comprise one of the polymers described above,for example, ethoxylated PEI, in combination with a polyalkylene glycol.When the second surfactant is AAS or AES, each of the particles mayfurther comprise from about 0.5% to about 20%, or from about 1% to about15%, or from about 2% to about 10% of a polyalkylene glycol, by totalweight of such each discrete particle. The polyalkylene glycol may be apolyethylene glycol with a weight average molecular weight ranging from500 to 20,000 Daltons, or from about 1000 to 15,000 Daltons, and or from2000 to 8000 Daltons.

Alkoxylated Polyalkyleneimine:

The alkoxylated polyalkyleneimine may have an empirical formula of(PEI)_(a)(CH₂CH₂O)_(b)(CH₂CH₂CH₂O)_(c), in which PEI is apolyethyleneimine core; a is the number average molecular weight(MW_(n)) of the PEI core prior to modification, which ranges from about100 to about 100,000 Daltons, or from about 200 to about 5000 Daltons,or from about 500 to about 1000 Daltons; b is the weight average numberof ethylene oxide (CH₂CH₂O) units per nitrogen atom in the PEI core,which ranges from 0 to about 60, or from about 1 to about 50, or fromabout 5 to about 40, or from about 10 to about 30; and c is the weightaverage number of propylene oxide (CH₂CH₂CH₂O) units per nitrogen atomin the PEI core, which ranges from 0 to about 60, or from 0 to about 40,or from 0 to about 30, or from 0 to about 20.

Ethylene Oxide-Propylene Oxide-Ethylene Oxide (EOx₁POyEOx₂) TriblockCopolymer:

In the ethylene oxide-propylene oxide-ethylene oxide (EOx₁POyEOx₂)triblock copolymer, each of x₁ and x₂ is in the range of about 2 toabout 140 and y is in the range of from about 15 to about 70. Theethylene oxide-propylene oxide-ethylene oxide (EOx₁POyEOx₂) triblockcopolymer preferably has an average propylene oxide chain length ofbetween 20 and 70, preferably between 30 and 60, more preferably between45 and 55 propylene oxide units.

Preferably, the ethylene oxide-propylene oxide-ethylene oxide(EOx₁POyEOx₂) triblock copolymer has a molecular weight of between about1000 and about 10,000 Daltons, preferably between about 1500 and about8000 Daltons, more preferably between about 2000 and about 7000 Daltons,even more preferably between about 2500 and about 5000 Daltons, mostpreferably between about 3500 and about 3800 Daltons.

Preferably, each ethylene oxide block or chain independently has anaverage chain length of between 2 and 90, preferably 3 and 50, morepreferably between 4 and 20 ethylene oxide units. Preferably, thecopolymer comprises between 10% and 90%, preferably between 15% and 50%,most preferably between 15% and 25% by weight of the copolymer of thecombined ethylene-oxide blocks. Most preferably the total ethylene oxidecontent is equally split over the two ethylene oxide blocks. Equallysplit herein means each ethylene oxide block comprising on averagebetween 40% and 60% preferably between 45% and 55%, even more preferablybetween 48% and 52%, most preferably 50% of the total number of ethyleneoxide units, the % of both ethylene oxide blocks adding up to 100%. Someethylene oxide-propylene oxide-ethylene oxide (EOx₁POyEOx₂) triblockcopolymer, where each of x₁ and x₂ is in the range of about 2 to about140 and y is in the range of from about 15 to about 70, improvecleaning.

Preferably the copolymer has a molecular weight between about 3500 andabout 3800 Daltons, a propylene oxide content between 45 and 55propylene oxide units, and an ethylene oxide content of between 4 and 20ethylene oxide units per ethylene oxide block.

Preferably, the ethylene oxide-propylene oxide-ethylene oxide(EOx₁POyEOx₂) triblock copolymer has a molecular weight of between 1000and 10,000 Daltons, preferably between 1500 and 8000 Daltons, morepreferably between 2000 and 7500 Daltons. Preferably, the copolymercomprises between 10% and 95%, preferably between 12% and 90%, mostpreferably between 15% and 85% by weight of the copolymer of thecombined ethylene-oxide blocks. Some ethylene oxide-propyleneoxide-ethylene oxide (EOx₁POyEOx₂) triblock copolymer, where each of x₁and x₂ is in the range of about 2 to about 140 and y is in the range offrom about 15 to about 70, improve dissolution.

Suitable ethylene oxide-propylene oxide-ethylene oxide triblockcopolymers are commercially available under the Pluronic PE series fromthe BASF company, or under the Tergitol L series from the Dow ChemicalCompany. A particularly suitable material is Pluronic PE 9200.

N,N,N′,N′-tetra(2-hydroxyethyl)ethylenediamine

N,N,N′,N′-tetra(2-hydroxyethyl)ethylenediamine is a suitable functionalrheology modifier, which also has chelant activity.

The size distribution of the particles, as characterized according tothe Granular Size Distribution Test Method, may have a D50 greater thanabout 150 μm and less than about 1600 μm, or a D50 greater than 205 μmand less than about 1000 μm, or a D50 greater than about 300 μm and aD90 less than about 850 μm, or a D50 greater than about 350 μm and lessthan about 700 μm.

The size distribution of the particle, as characterized according to theGranular Size Distribution Test Method, may have a D20 greater thanabout 150 μm and a D80 less than about 1400 μm, or a D20 greater thanabout 200 μm and a D80 less than about 1180 μm, or a D20 greater thanabout 250 μm and a D80 less than about 1000 μm.

The size distribution of the particle, as characterized according to theGranular Size Distribution Test Method, may have a D10 greater thanabout 150 μm and a D90 less than about 1400 μm, or a D10 greater thanabout 200 μm and a D90 less than about 1180 μm, or a D10 greater thanabout 250 μm and a D90 less than about 1000 μm.

The particles disclosed herein may optionally include one or more otheractive agents (e.g., adjunct detergent ingredient) for assisting orenhancing cleaning performance or to modify the aesthetics thereof.Illustrative examples of such adjunct detergent ingredients include: (1)inorganic and/or organic builders, such as carbonates (includingbicarbonates and sesquicarbonates), sulphates, phosphates (exemplifiedby the tripolyphosphates, pyrophosphates, and glassy polymericmeta-phosphates), phosphonates, phytic acid, silicates, zeolite,citrates, polycarboxylates and salts thereof (such as mellitic acid,succinic acid, oxydisuccinic acid, polymaleic acid, benzene1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and solublesalts thereof), ether hydroxypolycarboxylates, copolymers of maleicanhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, 3,3-dicarboxy-4-oxa-1,6-hexanedioates,polyacetic acids (such as ethylenediamine tetraacetic acid andnitrilotriacetic acid) and salts thereof, fatty acids (such as C₁₂-C₁₈monocarboxylic acids); (2) chelating agents, such as iron and/ormanganese-chelating agents selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein; (3) clay soilremoval/anti-redeposition agents, such as water-soluble ethoxylatedamines (particularly ethoxylated tetraethylene-pentamine); (4) polymericdispersing agents, such as polymeric polycarboxylates,acrylic/maleic-based copolymers and water-soluble salts thereof of,hydroxypropylacrylate, maleic/acrylic/vinyl alcohol terpolymers,polyaspartates and polyglutamates; (5) optical brighteners, whichinclude but are not limited to derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide,azoles, 5- and 6-membered-ring heterocycles, and the like; (6) sudssuppressors, such as monocarboxylic fatty acids and soluble saltsthereof, high molecular weight hydrocarbons (e.g., paraffins,haloparaffins, fatty acid esters, fatty acid esters of monovalentalcohols, aliphatic C₁₈-C₄₀ ketones, etc.), N-alkylated amino triazines,propylene oxide, monostearyl phosphates, silicones or derivativesthereof, secondary alcohols (e.g., 2-alkyl alkanols) and mixtures ofsuch alcohols with silicone oils; (7) suds boosters, such as C₁₀-C₁₆alkanolamides, C₁₀-C₁₄ monoethanol and diethanol amides, high sudsingsurfactants (e.g., amine oxides, betaines and sultaines), and solublemagnesium salts (e.g., MgCl₂, MgSO₄, and the like); (8) fabricsofteners, such as smectite clays, amine softeners and cationicsofteners; (9) dye transfer inhibiting agents, such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof; (10) enzymes, such as proteases,amylases, lipases, cellulases, and peroxidases, and mixtures thereof;(11) enzyme stabilizers, which include water-soluble sources of calciumand/or magnesium ions, boric acid or borates (such as boric oxide, boraxand other alkali metal borates); (12) bleaching agents, such aspercarbonates (e.g., sodium carbonate peroxyhydrate, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide),persulfates, perborates, magnesium monoperoxyphthalate hexahydrate, themagnesium salt of metachloro perbenzoic acid,4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid,6-nonylamino-6-oxoperoxycaproic acid, and photoactivated bleachingagents (e.g., sulfonated zinc and/or aluminum phthalocyanines); (13)bleach activators, such as nonanoyloxybenzene sulfonate (NOBS),tetraacetyl ethylene diamine (TAED), amido-derived bleach activatorsincluding (6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof,benzoxazin-type activators, acyl lactam activators (especially acylcaprolactams and acyl valerolactams); and (14) any other known detergentadjunct ingredients, including but not limited to carriers, hydrotropes,processing aids, dyes or pigments (especially hueing dyes), perfumes(including both neat perfumes and perfume microcapsules), and solidfillers.

Other Particles

In addition to the surfactant-containing particles describedhereinabove, the water-soluble unit dose articles described herein mayfurther contain other particles distributed throughout the fibrousstructure. For example, such other particles may include soluble and/orinsoluble material, where the insoluble material is dispersible inaqueous wash conditions to a suspension mean particle size that is lessthan about 20 microns.

The other particles may be a powder, granule, agglomerate, encapsulate,microcapsule, and/or prill. The other particles may be made using anumber of well-known methods in the art, such as spray-drying,agglomeration, extrusion, prilling, encapsulation, pastillation andcombinations thereof. The shape of the other particles can be in theform of spheres, rods, plates, tubes, squares, rectangles, discs, stars,fibers or have regular or irregular random forms.

The other particles may have a a D50 particle size of from about 150 urnto about 1600 μm as measured according to the Granular Size DistributionTest Method.

The other particles may be any solid, free-flowing particles, and mayinclude a mixture of chemically different particles, such as: surfactantparticles (those substantially free of the second surfactant), includingsurfactant agglomerates, surfactant extrudates, surfactant needles,surfactant noodles, surfactant flakes; phosphate particles; zeoliteparticles; silicate salt particles, especially sodium silicateparticles; carbonate salt particles, especially sodium carbonateparticles; polymer particles such as carboxylate polymer particles,cellulosic polymer particles, starch particles, polyester particles,polyamine particles, terephthalate polymer particles, polyethyleneglycol particles; aesthetic particles such as colored noodles, needles,lamellae particles and ring particles; enzyme particles such as proteasegranulates, amylase granulates, lipase granulates, cellulase granulates,mannanase granulates, pectate lyase granulates, xyloglucanasegranulates, bleaching enzyme granulates and co-granulates of any ofthese enzymes, these enzyme granulates may comprise sodium sulphate;bleach particles, such as percarbonate particles, especially coatedpercarbonate particles, such as percarbonate coated with carbonate salt,sulphate salt, silicate salt, borosilicate salt, or any combinationthereof, perborate particles, bleach activator particles such as tetraacetyl ethylene diamine particles and/or alkyl oxybenzene sulphonateparticles, bleach catalyst particles such as transition metal catalystparticles, and/or isoquinolinium bleach catalyst particles, pre-formedperacid particles, especially coated pre-formed peracid particles;filler particles such as sulphate salt particles and chloride particles;clay particles such as montmorillonite particles and particles of clayand silicone; flocculant particles such as polyethylene oxide particles;wax particles such as wax agglomerates; silicone particles, brightenerparticles; dye transfer inhibition particles; dye fixative particles;perfume particles such as perfume microcapsules and starch encapsulatedperfume accord particles, or pro-perfume particles such as Schiff basereaction product particles; hueing dye particles; chelant particles suchas chelant agglomerates; and any combination thereof.

Test Methods Thickness Test Method

Article thickness is measured by measuring the thickness caliper of thearticle using—Check-Line® (by Electromatic) digital thickness guage,Model # J-40-V, where the thickness is measured at the geometric centerof the article.

Basis Weight Test Method

Basis weight of a fibrous structure is measured on stacks of twelveusable units using a top loading analytical balance with a resolution of±0.001 g. The balance is protected from air drafts and otherdisturbances using a draft shield. A precision cutting die, measuring3.500 in ±0.0035 in by 3.500 in ±0.0035 in is used to prepare allsamples.

With a precision cutting die, cut the samples into squares. Combine thecut squares to form a stack twelve samples thick. Measure the mass ofthe sample stack and record the result to the nearest 0.001 g.

The Basis Weight is calculated in lbs/3000 ft² or g/m² as follows:

Basis Weight=(Mass of stack)/[(Area of 1 square in stack)×(No. ofsquares in stack)]

For example,

Basis Weight(lbs/3000 ft²)=[[Mass of stack (g)/453.6 (g/lbs)]/[12.25(in²)/144 (in²/ft²)×12]]×3000

or,

Basis Weight(g/m²)=Mass of stack (g)/[79.032 (cm²)/10,000 (cm²/m²)×12]

Report result to the nearest 0.1 lbs/3000 ft² or 0.1 g/m². Sampledimensions can be changed or varied using a similar precision cutter asmentioned above, so as at least 100 square inches of sample area instack.

Diameter Test Method

The diameter of a discrete fibrous element or a fibrous element within afibrous structure is determined by using a Scanning Electron Microscope(SEM) or an Optical Microscope and an image analysis software. Amagnification of 200 to 10,000 times is chosen such that the fibrouselements are suitably enlarged for measurement. When using the SEM, thesamples are sputtered with gold or a palladium compound to avoidelectric charging and vibrations of the fibrous element in the electronbeam. A manual procedure for determining the fibrous element diametersis used from the image (on monitor screen) taken with the SEM or theoptical microscope. Using a mouse and a cursor tool, the edge of arandomly selected fibrous element is sought and then measured across itswidth (i.e., perpendicular to fibrous element direction at that point)to the other edge of the fibrous element. A scaled and calibrated imageanalysis tool provides the scaling to get actual reading in μm. Forfibrous elements within a fibrous structure, several fibrous elementsare randomly selected across the sample of the fibrous structure usingthe SEM or the optical microscope. At least two portions of the fibrousstructure are cut and tested in this manner Altogether at least 100 suchmeasurements are made and then all data are recorded for statisticalanalysis. The recorded data are used to calculate average (mean) of thefibrous element diameters, standard deviation of the fibrous elementdiameters, and median of the fibrous element diameters.

Another useful statistic is the calculation of the amount of thepopulation of fibrous elements that is below a certain upper limit. Todetermine this statistic, the software is programmed to count how manyresults of the fibrous element diameters are below an upper limit andthat count (divided by total number of data and multiplied by 100%) isreported in percent as percent below the upper limit, such as percentbelow 1 micrometer diameter or %-submicron, for example. We denote themeasured diameter (in μm) of an individual circular fibrous element asdi.

In the case that the fibrous elements have non-circular cross-sections,the measurement of the fibrous element diameter is determined as and setequal to the hydraulic diameter which is four times the cross-sectionalarea of the fibrous element divided by the perimeter of thecross-section of the fibrous element (outer perimeter in case of hollowfibrous elements). The number-average diameter, alternatively averagediameter is calculated as:

$d_{num} = \frac{\sum\limits_{i = 1}^{n}d_{i}}{n}$

Granular Size Distribution Test Method

The granular size distribution test is conducted to determinecharacteristic sizes of particles. It is conducted using ASTM D 502-89,“Standard Test Method for Particle Size of Soaps and Other Detergents”,approved May 26, 1989, with a further specification for sieve sizes andsieve time used in the analysis. Following section 7, “Procedure usingmachine-sieving method,” a nest of clean dry sieves containing U.S.Standard (ASTM E 11) sieves #4 (4.75 mm), #6 (3.35 mm), #8 (2.36 mm),#12 (1.7 mm), #16 (1.18 mm), #20 (850 μm), #30 (600 μm), #40 (425 μm),#50 (300 μm), #70 (212 μm), #100 (150 μm) is required to cover the rangeof particle sizes referenced herein. The prescribed Machine-SievingMethod is used with the above sieve nest. A suitable sieve-shakingmachine can be obtained from W.S. Tyler Company, Ohio, U.S.A. Thesieve-shaking test sample is approximately 100 grams and is shaken for 5minutes.

The data are plotted on a semi-log plot with the micron size opening ofeach sieve plotted against the logarithmic abscissa and the cumulativemass percent (Q₃) plotted against the linear ordinate. An example of theabove data representation is given in ISO 9276-1:1998, “Representationof results of particle size analysis—Part 1: Graphical Representation”,Figure A.4. A characteristic particle size (Dx), for this invention, isdefined as the abscissa value at the point where the cumulative masspercent is equal to x percent, and is calculated by a straight-lineinterpolation between the data points directly above (a) and below (b)the x % value using the following equation:

Dx=10{circumflex over ( )}[Log(Da)−(Log(Da)−Log(Db))*(Qa−x %)/(Qa−Qb)]

where Log is the base-10 logarithm, Qa and Qb are the cumulative masspercentile values of the measured data immediately above and below thex^(th) percentile, respectively; and Da and Db are the micron sieve sizevalues corresponding to these data.

Example Data and Calculations:

sieve weight on cumulative mass % size (um) sieve (g) finer (CMPF) 47500  100% 3350 0  100% 2360 0  100% 1700 0  100% 1180 0.68 99.3% 850 10.4089.0% 600 28.73 60.3% 425 27.97 32.4% 300 17.20 15.2% 212 8.42  6.8% 1504.00  2.8% Pan 2.84  0.0%

For D10 (x=10%), the micron screen size where CMPF is immediately above10% (Da) is 300 μm, the screen below (Db) is 212 μm. The cumulative massimmediately above 10% (Qa) is 15.2%, below (Qb) is 6.8%.

D10=10{circumflex over( )}[Log(300)−(Log(300)−Log(212))*(15.2%−10%)/(15.2%−6.8%)]=242 μm

For D50 (x=50%), the micron screen size where CMPF is immediately above50% (Da) is 1180 μm, the screen below (Db) is 850 μm. The cumulativemass immediately above 90% (Qa) is 99.3%, below (Qb) is 89.0%.

D50=10{circumflex over( )}[Log(600)−(Log(600)−Log(425))*(60.3%−50%)/(60.3%−32.4%)]=528 μm

For D90 (x=90%), the micron screen size where CMPF is immediately above90% (Da) is 600 μm, the screen below (Db) is 425 μm. The cumulative massimmediately above 50% (Qa) is 60.3%, below (Qb) is 32.4%.

D90=10{circumflex over( )}[Log(1180)−(Log(1180)−Log(850))*(99.3%−90%)/(99.3%−89.0%)]=878 μm

Shear Viscosity Test Method

The shear viscosity of a concentrated perfume composition of the presentdisclosure is measured using a capillary rheometer, Goettfert Rheograph6000, manufactured by Goettfert USA of Rock Hill S.C., USA. Themeasurements are conducted using a capillary die having a diameter D of1.0 mm and a length L of 30 mm (i.e., L/D=30). The die is attached tothe lower end of the rheometer's 20 mm barrel, which is held at a dietest temperature of 75° C. A preheated to die test temperature, 60 gsample of the concentrated perfume composition is loaded into the barrelsection of the rheometer. Rid the sample of any entrapped air. Push thesample from the barrel through the capillary die at a set of chosenrates 1,000-10,000 seconds⁻¹. An apparent shear viscosity can becalculated with the rheometer's software from the pressure drop thesample experiences as it goes from the barrel through the capillary dieand the flow rate of the sample through the capillary die. The log(apparent shear viscosity) can be plotted against log (shear rate) andthe plot can be fitted by the power law, according to the formulaη=Kγ^(n−1), wherein K is the material's viscosity constant, n is thematerial's thinning index and γ is the shear rate. The reported apparentshear viscosity of the concentrated perfume composition herein iscalculated from an interpolation to a shear rate of 3,000 sec⁻¹ usingthe power law relation.

Onset of Melt Test Method

Onset of melt is determined using the Onset of Melt Test Method asfollows. Differential Scanning calorimetry (DSC) is used to quantify thetemperature at which the onset of melt occurs for the peak melttransition of any given composition of particles to be tested. The melttemperature measurements are made using a high-quality DSC instrumentwith accompanying software and nitrogen purge capability, such as TAInstruments' model Discovery DSC (TA Instruments Inc./WatersCorporation, New Castle, Del., U.S.A.). A calibration check is conductedusing an Indium standard sample. The DSC instrument is consideredsuitable to conduct the test if the onset of melt temperature measuredfor the Indium standard sample is within the range of 156.3-157.3° C.

A uniform test sample is prepared by obtaining at least 5 g ofparticles, which are then pulverised via milling into powder form usingan analytical milling device, such as the IKA basic analytical millmodel A11 B S1 (IKA-Werke GmbH & Co. KG, Staufen im Breisgau, Germany)The milled sample is subsequently sieved through a clean stainless steelsieve with sieve mesh size openings of nominally 1 mm in diameter (e.g.number 18 mesh size). For each sample to be tested, at least tworeplicate samples are independently milled and measured. A sample of themilled material weighing approximately 5 mg is placed into the bottom ofa hermetic aluminium DSC sample pan, and the sample is spread out tocover the base of the pan. A hermetic aluminium lid is placed on thesample pan, and the lid is sealed with a sample encapsulating press toprevent evaporation or weight loss during the measurement process. TheDSC measurements are conducted relative to a reference standard. Anempty aluminum DSC sample pan used as the reference standard, in orderto measure the delta in heat adsorption of the sample-containing panversus the empty reference pan.

The DSC instrument is set up to analyze samples using the followingcycle configuration selections: Sample Purge Gas is nitrogen set at 50mL/min; Sampling Interval is set at 0.1 s/point; Equilibrate is set at−20.00° C.; Isothermal Hold is set at 1 min. Data is collected during asingle heating cycle using the settings: Ramp is set at 10.00° C./min to90.00° C.; and Isothermal Hold is set at 90.00° C. for 1 min. A sealedsample pan containing a replicate test sample is carefully loaded intothe instrument, as is an empty reference pan. The DSC analysis cyclespecified above is conducted and the output data is assessed. The dataacquired during the DSC heating cycle is typically plotted withTemperature on the X-axis (in ° C.) and Heat Flow normalized to sampleweight (in W/g) on the Y-axis, such that melting points appear asdownward (endothermic) peaks since they absorb energy.

A melt transition onset temperature is the temperature at which adeflection is first observed from the baseline previously establishedfor the melt temperature of interest. The Peak Melt temperature is thespecific temperature that requires the largest observed differentialenergy to transition the sample from a solid phase to a melt phase,during the specified DSC heating cycle. For the purpose of thisinvention, the Onset of Melt temperature is defined as the melttransition onset temperature for the Peak Melt temperature. Additionalgeneral information on the DSC technique may be found in the industrystandard method ASTM D3418-03—Transition Temperatures of Polymers byDSC.

Using the DSC instrument software, two points are manually defined asthe “Start and Stop Integration” baseline limits. The two pointsselected are on flat regions of the baseline to the left and rightsides, respectively, of the melt transition peak detected. This definedarea is then used to determine the peak temperature (T) which can beused to report the Peak Melt Temperature. The Onset of Melt temperaturefor the Peak Melt temperature is then identified by the instrumentsoftware.

The Onset of Melt temperature reported is the average result (in ° C.)from the replicate samples.

Dissolution Test Method

Apparatus and Materials:

-   -   600 mL Beaker    -   Magnetic Stirrer 56 (Labline Model No. 1250 or equivalent)    -   Magnetic Stirring Rod 58 (5 cm)    -   Thermometer (1 to 100° C.+/−1° C.)    -   Cutting Die—Stainless Steel cutting die with dimensions 3.8        cm×3.2 cm    -   Timer (0-3,600 seconds or 1 hour), accurate to the nearest        second. Timer used should have sufficient total time measurement        range if sample exhibits dissolution time greater than 3,600        seconds. However, timer needs to be accurate to the nearest        second.    -   Polaroid 35 mm Slide Mount (commercially available from Polaroid        Corporation or equivalent)    -   35 mm Slide Mount Holder (or equivalent)    -   City of Cincinnati Water or equivalent having the following        properties: Total Hardness=155 mg/L as CaCO₃; Calcium        content=33.2 mg/L; Magnesium content=17.5 mg/L; Phosphate        content=0.0462.

Equilibrate samples in constant temperature and humidity environment of23° C.±1.0° C. and 50% RH±2% for at least 2 hours. Measure the basisweight of the fibrous structure sample to be measured using Basis WeightTest Method defined herein. Cut three dissolution test specimens fromthe article, for example fibrous structure sample using cutting die (3.8cm×3.2 cm), so it fits within the 35 mm Slide Mount, which has an openarea dimensions 24×36 mm Lock each specimen in a separate 35 mm slidemount. Place magnetic stirring rod into the 600 mL beaker. Turn on thecity water tap flow (or equivalent) and measure water temperature withthermometer and, if necessary, adjust the hot or cold water to maintainit at the testing temperature. Testing temperature is 15° C.±1° C.water. Once at testing temperature, fill beaker with 500 mL±5 mL of the15° C.±1° C. city water. Place full beaker 54 on magnetic stirrer, turnon stirrer, and adjust stir speed until a vortex develops and the bottomof the vortex is at the 400 mL mark on the beaker. Secure the 35 mmslide mount in the alligator clamp of the 35 mm slide mount holder suchthat the long end of the slide mount is parallel to the water surface.The alligator clamp should be positioned in the middle of the long endof the slide mount. The depth adjuster of the holder should be set sothat the distance between the bottom of the depth adjuster and thebottom of the alligator clip is ˜11+/−0.125 inches. This set up willposition the sample surface perpendicular to the flow of the water. Inone motion, drop the secured slide and clamp into the water and startthe timer. The sample is dropped so that the sample is centered in thebeaker. Disintegration occurs when the nonwoven structure breaks apart.Record this as the disintegration time. When all of the visible nonwovenstructure is released from the slide mount, raise the slide out of thewater while continuing the monitor the solution for undissolved nonwovenstructure fragments. Dissolution occurs when all nonwoven structurefragments are no longer visible. Record this as the dissolution time.

Three replicates of each sample are run and the average disintegrationand dissolution times are recorded. Average disintegration anddissolution times are in units of seconds.

The average disintegration and dissolution times can be normalized forbasis weight by dividing each by the sample basis weight as determinedby the Basis Weight Method defined herein. Basis weight normalizeddisintegration and dissolution times are in units of seconds/gsm ofsample (s/(g/m²)).

EXAMPLES Example 1

As illustrated in FIG. 3, a first layer of fibrous elements is spunusing a first spinning beam and collected on a forming belt. The formingbelt having the first layer of fibers then passes under a secondspinning beam that is modified with a particle addition system. Theparticle addition system is capable of substantially injecting particlestoward a landing zone on the forming belt that is directly under thefibrous elements from the second spinning beam. Suitable particleaddition systems may be assembled from a particle feeder, such as avibratory, belt or screw feeder, and an injection system, such as an airknife or other fluidized conveying system. In order to aid in aconsistent distribution of particles in the cross direction, theparticles are preferably fed across about the same width as the spinningdie to ensure particles are delivered across the full width of thecomposite structure. Preferably, the particle feeder is completelyenclosed with the exception of the exit to minimize disruption of theparticle feed. The co-impingement of particles and fibrous elements onthe forming belt under the second spinning beam creates a compositestructure where the particle packing is dilated and fibers substantiallyinter-penetrate the inter-particle porosity.

Table 1 below sets forth non-limiting examples of dried fibercompositions of the present invention, which is used to make the fibrouselements. To make the fibrous elements, an aqueous solution, preferablyhaving about 45% to 60% solids content, is processed through one or morespinning beams as shown in FIG. 3. A suitable spinning beam comprises acapillary die with attenuation airflow, along with drying airflowsuitable to substantially dry the attenuated fibers before theirimpingement on the forming belt.

Preferably, a blend of Polyvinyl Alcohol (PVOH) and Polyethylene Oxide(PEO) is used in a blend ratio of from about 5:1 to about 10:1. The PEOportion preferably comprises a blend of molecular weights from about100,000 to 2,000,000 g/mol.

TABLE 1 Fiber (F) Compositions Fiber Formulation (%) F1 F2 F3 LAS 47.243.1 51.7 AS 23.6 21.6 12.9 PVOH + PEO 26.2 32.3 32.3 Moist + misc. 3.03.0 3.0 Total 100 100 100

Table 2 below sets forth non-limiting examples of a particlecompositions of the present invention. Particles may be made by avariety of suitable processes including milling, spray-drying,agglomeration, extrusion, prilling, encapsulation, pastillization andany combination thereof. One or more particles may be mixed togetherbefore adding to the composite structure.

TABLE 2 Particle (P) Compositions: Particle Formulation (%) P1 P2 P3 P4P5 P6 P7 P8 P9 LAS 0.0 6.3 9.5 8.6 10.8 17.2 19.9 19.2 20.8 AS 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 0.0 AES 24.0 21.8 21.6 26.0 21.6 34.3 26.6 25.727.7 Sodium Carb. 18.0 15.9 15.3 14.4 10.0 21.6 21.3 20.6 22.2 Zeolite-A54.2 33.5 32.0 46.9 51.8 0.0 0.0 0.0 0.0 Chelant 0.0 0.0 0.0 0.0 0.0 0.00.0 3.5 0.0 PE20 0.0 8.6 3.7 1.0 3.5 3.5 3.5 3.4 3.4 Disp. Poly 0.0 4.10.0 0.0 0.0 0.0 8.4 8.1 8.4 PEG4k 0.8 0.0 8.2 0.0 0.0 0.0 0.0 0.0 0.0PVOH + PEO 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.7 Moist + misc. 3.0 9.8 9.83.1 2.3 23.4 20.3 19.6 15.8 Total 100 100 100 100 100 100 100 100 100

Product chasses are exemplified in Table 3, providing structural detailfor product chasses by fiber and particle components (from Tables 1 and2, respectively), with the net chassis composition for the product. Notethat other product adjunct materials such as perfume, enzymes, sudssuppressor, bleaching agents, etc. may be added to a chassis.

TABLE 3 Product Chasses (C) Chassis C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11C12 C13 C14 Fiber type F1 F2 F2 F2 F3 F2 F2 F2 F2 F2 F2 F2 F2 F2 Fiberwt % 28% 28% 28% 27% 27% 27% 19% 16% 27% 23% 23% 23% 23% 19% Particletype P1 P1 P2 P3 P3 P3 P3 P3 P4 P5 P6 P7 P8 P9 Particle wt % 72% 72% 72%73% 73% 73% 81% 84% 73% 77% 77% 77% 77% 81% Basis wt, gsm 2803 2803 28032879 2879 2879 4091 4848 2848 2803 2803 2803 2803 2803 Formulation,g/dose: LAS 2.43 2.22 3.06 3.53 3.97 3.53 4.29 4.76 3.39 3.37 4.28 4.674.57 4.65 AS 1.22 1.11 1.11 1.11 0.67 1.11 1.11 1.11 1.11 0.92 0.92 0.920.92 0.78 AES 3.20 3.20 2.91 2.99 2.99 2.99 4.72 5.79 3.55 3.08 4.893.79 3.66 4.13 PE20 0.00 0.00 1.15 0.51 0.51 0.51 0.80 0.98 0.14 0.500.50 0.50 0.48 0.51 PEG4k 0.11 0.11 0.00 1.14 1.14 1.14 1.80 2.21 0.000.00 0.00 0.00 0.00 0.00 Disp poly 0.00 0.00 0.55 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 1.20 1.16 1.25 Sodium Carb. 2.40 2.40 2.12 2.12 2.122.12 3.34 4.11 1.96 1.43 3.08 3.04 2.93 3.31 Zeolite-A 7.24 7.24 4.474.43 4.43 4.43 6.99 8.58 6.41 7.38 0.00 0.00 0.00 0.00 Chelant 0.00 0.000.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.50 0.00 Silica 0.000.00 0.91 0.93 0.93 0.93 1.47 1.80 0.00 0.00 2.88 2.45 2.37 1.83 PVOH +PEO 1.35 1.66 1.66 1.66 1.66 1.66 1.66 1.66 1.66 1.37 1.37 1.37 1.371.42 moist & misc 0.55 0.55 0.56 0.58 0.58 0.58 0.83 0.99 0.57 0.46 0.580.57 0.55 0.63 Total chassis 18.5 18.5 18.5 19.0 19.0 19.0 27.0 32.018.8 18.5 18.5 18.5 18.5 18.5

Raw Materials for Example 1

LAS is linear alkylbenzenesulfonate having an average aliphatic carbonchain length C₁₁-C₁₂ supplied by Stepan, Northfield, Ill., USA orHuntsman Corp. HLAS is acid form. AES is C₁₂₋₁₄ alkyl ethoxy (3)sulfate, C₁₄₋₁₅ alkyl ethoxy (2.5) sulfate, C₁₂₋₁₅ alkyl ethoxy (1.8)sulfate, C₁₂₋₁₅ alkyl ethoxy (1.0) sulfate, or C₁₄₋₁₅ alkyl ethoxy (1.0)sulfate supplied by Stepan, Northfield, Ill., USA or Shell Chemicals,Houston, Tex., USA.AS is a C₁₂₋₁₄ sulfate, supplied by Stepan, Northfield, Ill., USA,and/or a mid-branched alkyl sulfate.Dispersant polymer (Disp poly) is molecular weight 70,000 andacrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, GermanyEthoxylated Polyethylenimine (PE20) is a 600 g/mol molecular weightpolyethylenimine core with 20 ethoxylate groups per —NH. Available fromBASF (Ludwigshafen, Germany).Chelant is diethylenetriaminepentaacetic acid (DTPA) available fromAkzo-Nobel (Amsterdam, Netherlands)Polyethylene glycol 4000 g/mol molecular weight (PEG4k) is availablefrom Dow Chemical (Midland, Mich., USA)Suitable grades of Polyvinyl Alcohol (PVOH) are available from KurarayPoval (Houston Tex., USA), preferably Kuraray Poval Grade 505.Suitable grades of Polyethlyene oxide (PEO) are available from DowChemical (Midland, Mich., USA), including POLYOX WSR N10 and POLYOX WSRN60K.

Table 4 below sets forth non-limiting examples of concentrated perfumecompositions of the present disclosure. To make the concentrated perfumecomposition, perfume is mixed with the quaternary ammonium compound andoptionally a hydrophobic ester.

TABLE 4 Concentrated Perfume Compositions Weight % of water-soluble unitdose article Perfume A 1.35% Perfume B 1.39% Perfume C 1.36% Perfume D1.38 Quaternary 3.5%-8.0% 3.5%-8.0% 3.5%-8.0% 3.5%-8.0% ammoniumcompound- Perfume A, B, C, or D

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A water-soluble unit dose article comprising awater-soluble fibrous first ply superposed to a water-soluble fibroussecond ply, wherein a concentrated perfume composition is positionedbetween the superposed plies, the concentrated perfume compositioncomprising from about 55% to about 90% by weight of the composition of aperfume and from about 10% to about 45% by weight of the composition ofan oil-binding agent.
 2. The water-soluble unit dose article accordingto claim 1, wherein the oil-binding agent is a quaternary ammoniumcompound, preferably a quaternary ammonium compound having an IodineValue of from about 1 to about
 30. 3. The water-soluble unit dosearticle according to claim 1, wherein the oil-binding agent is aquaternary ammonium compound selected from the group consisting ofdiester quaternary ammonium compounds, diethyl ester quaternary ammoniumcompounds, and mixtures thereof.
 4. The water-soluble unit dose articleaccording to claim 1, wherein the oil-binding agent is a quaternaryammonium compound of Formula (II):{R² _((4-m))—N+-[X—Y—R¹]_(m)}A-  Formula (II) wherein: m is 1, 2 or 3;each R¹ is independently a hydrocarbyl or branched hydrocarbyl group;each R² is independently a C₁-C₃ alkyl or hydroxyalkyl group; each X isindependently (CH₂)n, CH₂—CH(CH₃)—, or CH—(CH₃)—CH₂— and each n isindependently 1, 2, 3 or 4; each Y is independently —O—(O)C— or—C(O)—O—; A- is independently selected from the group consisting ofchloride, methyl sulfate, and ethyl sulfate; and when Y is —O—(O)C—, thesum of carbons in each R¹ is from 13 to
 21. 5. The water-soluble unitdose article according to claim 1, wherein the oil-binding agent isselected from the group consisting of diethylester dimethyl ammoniumchloride, bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fattyacid ester and isomers thereof, N,N,N-tri(2-hydroxyethyl)-N-methylammonium methylsulfate fatty acid ester, polyglyceryl-6 dipalmitate,N,N-bis(2-hydroxyethyl)-N,N-dimethyl ammonium chloride fatty acid ester,and mixtures thereof.
 6. The water-soluble unit dose article accordingto claim 1, wherein the concentrated perfume composition furthercomprises from about 1% to about 10% by weight of the composition of ahydrophobic ester, preferably the hydrophobic ester is an alkyl ester,more preferably an alkyl ester of Formula (I):

R₁: linear or branched C12-C22 alkyl R₂: linear or branched C2-C8 alkyl.7. The water-soluble unit dose article according to claim 1, wherein thehydrophobic ester is selected from the group consisting of isopropyllaureate, isopropyl myristate, isopropyl palmitate, and mixturesthereof.
 8. The water-soluble unit dose article according to claim 1,wherein the water-soluble unit dose article has less than about 15% byweight water.
 9. The water-soluble unit dose article according to claim1, wherein the first ply comprises at least two layers, a first layerand a second layer, the first layer facing the second layer, wherein thesecond ply comprises at least two layers, a third layer and a fourthlayer, the third layer facing the fourth layer, wherein said first layeris oriented towards a first ply belt side and said second layer isoriented towards a first ply air side, wherein said first ply air sideis opposite said first ply belt side, wherein said third layer isoriented towards a second ply belt side and said fourth layer isoriented towards a second ply air side, wherein said second ply air sideis opposite said second ply belt side, wherein said first ply belt sideand said second ply belt side face away from one another, and whereinsaid concentrated perfume composition is positioned between the secondlayer and the fourth layer.
 10. The water-soluble unit dose articleaccording to claim 9, wherein the first layer and the third layer aresubstantially free of the concentrated perfume composition.
 11. Thewater-soluble unit dose article according to claim 1, wherein thewater-soluble unit dose article further comprises a plurality ofparticles, preferably at least one of the particles comprises an activeagent selected from the group consisting of a surfactant, a structurant,a builder, a polymeric dispersing agent, an enzyme, an enzymestabilizer, a bleach system, a brightener, a hueing agent, a chelatingagent, a suds suppressor, a conditioning agent, a humectant, a perfume,a perfume microcapsule, a filler or carrier, an alkalinity system, a pHcontrol system, a buffer, an alkanolamine, mosquito repellant, andmixtures thereof.
 12. The water-soluble unit dose article according toany claim 1, wherein the water-soluble unit dose article has a BasisWeight of from about 500 grams/m2 to about 5,000 grams/m2 as measuredaccording to the Basis Weight Test Method described herein.
 13. Thewater-soluble unit dose article according to claim 1, wherein thewater-soluble unit dose article has a width from about 1 cm to about 11cm; a length from about 1 cm to about 20 cm; and a height from about0.01 mm to about 50 mm.
 14. The water-soluble unit dose articleaccording to claim 1, wherein the water-soluble unit dose articlefurther comprises a third ply, wherein the first ply, the second ply,and the third ply are superposed with one another so that the third plyis between the first ply and the second ply.
 15. The water-soluble unitdose article according to claim 14, wherein the concentrated perfumecomposition is positioned between the third ply and the first ply and/orbetween the third ply and the second ply.
 16. The water-soluble unitdose article according to claim 14, wherein the third ply comprises atleast two layers, a fifth layer and a sixth layer, the fifth layerfacing the sixth layer, wherein said third ply has a third ply belt sideand a third ply air side opposite the third ply belt side, wherein saidfifth layer is oriented towards a third ply belt side and said sixthlayer is oriented towards a third ply air side, wherein said third plyair side is opposite said third ply belt side.
 17. The water-solubleunit dose article according to claim 1, wherein the concentrated perfumecomposition has a viscosity of from about 1 Pa-s to about 25 Pa-s whenmeasured at 10 s⁻¹ at 20° C. as determined according to the ShearViscosity Test Method described herein.
 18. The water-soluble unit dosearticle of claim 1, wherein the concentrated perfume composition has aviscosity of from about 4 Pa-s to about 200 Pa-s when measured at 1 s⁻¹at 20° C. as determined according to the Shear Viscosity Test Methoddescribed herein and wherein the concentrated perfume composition has anonset of melt of from about 5° C. to about 25° C. as determinedaccording to the Differential calorimetry Test Method described herein.19. A process for manufacturing a water-soluble unit dose articlecomprising the steps of: providing a water soluble fibrous first ply;providing a water soluble fibrous second ply, preferably formed on asurface other than said first ply, wherein said second ply is separatefrom said first ply; providing a concentrated perfume compositionaccording to any one of the preceding claims; placing said concentratedperfume composition on one or both of said first ply and said secondply; superposing said first ply and said second ply so that saidconcentrated perfume composition is between said first ply and saidsecond ply; and joining a first portion of said first ply to a secondportion of said second ply to form said water soluble unit dose article.